JP2018146978A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition that can be uniformly applied on the whole surface of a substrate by a spin coating method even in a smaller discharge mass and gives excellent in-plane uniformity of the obtained coating film and a constant film thickness in an edge portion of the substrate.SOLUTION: A photosensitive resin composition for spin coating is provided, which comprises (A) an alkali-soluble resin, (B) a photoacid generator, and (C) a solvent having a vapor pressure of 10 Pa to 250 Pa at 25°C and a density of 0.7 g/cmto 1.02 g/cmat 25°C. The photosensitive resin composition for spin coating has a density of 0.75 g/cmto 1.1 g/cmat 25°C; and the photosensitive resin composition for spin coating has a viscosity of 0.5 Pa s to 2 Pa s at 25°C.SELECTED DRAWING: None

Description

  The present invention relates to an insulating material for electronic parts, and a photosensitive resin composition used for forming relief patterns such as a passivation film, a buffer coat film, and an interlayer insulating film in a semiconductor device.

  The material for the surface protective film and the interlayer insulating film of the semiconductor device includes an alkaline aqueous solution-soluble hydroxypolyamide, for example, polybenzoxazole (hereinafter also referred to as “PBO”) precursor and photosensitive diazoquinone, which becomes a heat resistant resin after curing. A photoacid generator such as a compound is mixed with a solvent such as γ-butyllactone (hereinafter referred to as “GBL”) to prepare a varnish of a PBO precursor composition, and this PBO precursor composition is used as a positive photosensitive resin. A method for use as a composition is disclosed in Patent Document 1, for example.

  In the process of manufacturing a semiconductor device, generally, the varnish of the precursor composition is applied to a substrate such as a silicon wafer by a spin coating method, patterned with actinic rays, developed, and heat polybenzoxazolized As a result, it is possible to easily form a surface protective film, an interlayer insulating film, or the like which becomes a part of the semiconductor device.

  In recent years, low-cost production has been strongly demanded for dynamic random access memory or NAND flash memory, which is a kind of semiconductor memory. Therefore, even in the process of forming the surface protective film of the semiconductor memory, it is strongly required to form a uniform surface protective film at a low cost.

  As one of the techniques, a method of reducing the amount of the photosensitive resin composition used when applying the photosensitive resin composition on a substrate is disclosed (Patent Document 2).

  Moreover, the photosensitive resin composition which is excellent in the film thickness uniformity at the time of thin film formation or the covering property of a board | substrate edge part is illustrated (patent document 3).

JP 63-096162 A JP 2004-153262 A JP 2007-86215 A

  However, in the method described in Patent Document 2, since the number of revolutions is extremely high, it is difficult to control the film thickness, and there are problems that air bubbles easily enter.

  In addition, the photosensitive resin composition described in Patent Document 3 has room for improvement in terms of discharge mass, although the film thickness uniformity at the time of thin film formation or the coverage of the substrate edge portion is improved.

  Therefore, the problem of the present invention is that even with a smaller discharge mass, it can be uniformly coated on the entire surface by a spin coating method, has excellent in-plane uniformity of the coating film, and is a film on the edge of the substrate. The object is to provide a photosensitive resin composition having a constant thickness.

As a result of intensive studies in view of the above-described problems of the prior art, the present inventors have obtained a photosensitive resin composition containing an alkali-soluble resin, a photoacid generator, and a specific solvent, It has been found that a photosensitive resin composition that solves the above-mentioned problems can be obtained by adjusting the density and viscosity at 25 ° C. of the composition to a specific range, and the present invention has been made.
That is, the present invention is as follows.

[1] (A) Alkali-soluble resin;
The solvent and (C) vapor at 25 ° C. pressure is 10Pa～250Pa, and density at 25 ° C. is ^{0.7g / cm 3 ~1.02g / cm 3} ; (B) a photoacid generator;
A spin-coating a photosensitive resin composition comprising, density at 25 ° C. of the spin-coating a photosensitive resin composition ^is a ^{0.75g / cm 3 ~1.1g / cm 3} , and the spin-coating The photosensitive resin composition for spin coating, wherein the photosensitive resin composition for coating has a viscosity at 25 ° C. of 0.5 Pa · s to 2 Pa · s.

[2] The (C) Density of solvent ^{is 0.8g / cm 3 ~0.95g / cm 3} , a spinning photosensitive resin composition according to [1].

  [3] The photosensitive resin composition for spin coating contains 30% by mass to 100% by mass of the solvent (C) with respect to the total mass of all the solvents contained in the photosensitive resin composition for spin coating. A photosensitive resin composition for spin coating according to [1] or [2].

  [4] The photosensitivity for spin coating according to any one of [1] to [3], wherein the solvent (C) is at least one selected from the group consisting of ketone, ether, alcohol, and glycol. Resin composition.

｛式中、Ｒ_１及びＲ_２は、それぞれ独立に、炭素原子数１〜９のアルキル基であり、そしてＲ_１とＲ_２の炭素原子数の和が、７〜１０である。｝

｛式中、Ｒ_３及びＲ_４は、それぞれ独立に、炭素原子数１〜１１のアルキル基であり、そしてＲ_３とＲ_４の炭素原子数の和が、９〜１２である。｝

｛式中、Ｒ_５は、炭素原子数５〜１０のアルキル基である。｝

｛式中、Ｒ_６及びＲ_７は、それぞれ独立に、水素原子、炭素原子数１〜５のアルキル基、又は下記一般式（５）：

（式中、Ｒ_９は、炭素原子数１〜５のアルキル基を表す）
で表される基Ｘを表すが、Ｒ_６及びＲ_７の両方が基Ｘになることはなく、Ｒ_８は、水素原子又は炭素数１若しくは２のアルキル基を表し、そしてｎ５は、１≦ｎ５≦３を満たす数である。｝
で表される化合物から成る群から選択される少なくとも１つである、［１］〜［４］のいずれか一項に記載のスピンコート用感光性樹脂組成物。 [5] The solvent (C) is represented by the following general formulas (1) to (4):

{In the formula, R ₁ and R ₂ are each independently an alkyl group having 1 to 9 carbon atoms, and the sum of the carbon atoms of R ₁ and R ₂ is 7 to 10. }

{In the formula, R ₃ and R ₄ are each independently an alkyl group having 1 to 11 carbon atoms, and the sum of the number of carbon atoms of R ₃ and R ₄ is 9 to 12. }

{Wherein R ₅ is an alkyl group having 5 to 10 carbon atoms. }

{In the formula, R ₆ and R ₇ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or the following general formula (5):

(Wherein R ₉ represents an alkyl group having 1 to 5 carbon atoms)
In which R ₆ and R ₇ are not both X, R ₈ represents a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, and n5 represents 1 ≦ It is a number satisfying n5 ≦ 3. }
The photosensitive resin composition for spin coating according to any one of [1] to [4], which is at least one selected from the group consisting of compounds represented by:

  [6] The solvent (C) is 2-octanone, 2-nonanone, diisobutyl ketone, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl. The photosensitive resin composition for spin coating according to any one of [1] to [5], which is at least one selected from the group consisting of ether, dipropylene glycol dimethyl ether, and dipropylene glycol methyl propyl ether. .

  [7] The (A) alkali-soluble resin is at least one selected from the group consisting of an alkali-soluble polyimide, a polyimide precursor, a polybenzoxazole precursor, and a phenol resin, [1] to [6] The photosensitive resin composition for spin coating as described in any one of Claims.

｛式中、Ｘ_１及びＹ_１は、各々独立に、２〜６０個の炭素原子を有する２〜８価の有機基を表し、Ｒ_１０及びＲ_１１は、各々独立に、水素原子又は炭素原子数１〜１０のアルキル基を表し、ｍ１は、１〜１０００の整数であり、ｎ１〜ｎ４は、それぞれ独立に、０〜４の整数であり、ｎ１及びｎ３は、０≦（ｎ１＋ｎ３）≦６を満たし、ｎ２及びｎ４は、０≦（ｎ２＋ｎ４）≦６を満たし、そしてｎ１〜ｎ４の全てが０になることはない。｝
で表される樹脂及び／又はフェノール樹脂を含む、［１］〜［７］のいずれか一項に記載のスピンコート用感光性樹脂組成物。 [8] The (A) alkali-soluble resin is represented by the following general formula (6):

{Wherein, X ₁ and Y ₁ each independently represent a 2 to 8 valent organic group having 2 to 60 carbon atoms, and R ₁₀ and R ₁₁ each independently represent a hydrogen atom or a carbon atom. Represents an alkyl group of formulas 1 to 10, m1 is an integer of 1 to 1000, n1 to n4 are each independently an integer of 0 to 4, and n1 and n3 are 0 ≦ (n1 + n3) ≦ 6. N2 and n4 satisfy 0 ≦ (n2 + n4) ≦ 6, and n1 to n4 do not all become zero. }
The photosensitive resin composition for spin coating as described in any one of [1]-[7] containing the resin and / or phenol resin which are represented by these.

  [9] The spin according to [8], wherein the (A) alkali-soluble resin contains 50 parts by mass to 150 parts by mass of a phenol resin with respect to 100 parts by mass of the resin represented by the general formula (6). Photosensitive resin composition for coating.

  [10] The photosensitive resin composition for spin coating according to any one of [1] to [9], wherein the (B) photoacid generator is a quinonediazide compound.

[11] The following:
(A) The photosensitive resin composition for spin coating according to any one of [1] to [10] is spin-coated on a substrate to form a photosensitive resin layer or a photosensitive film on the substrate. Process,
(B) a step of exposing the photosensitive resin layer or the photosensitive film;
(C) A cured relief pattern comprising a step of removing a exposed portion or an unexposed portion of the photosensitive resin layer or photosensitive film with a developer to obtain a relief pattern; and (d) a step of heating the relief pattern. Manufacturing method.

  [12] A cured relief pattern obtained by the method according to [11].

  [13] A semiconductor device comprising a semiconductor element and a cured film provided on the semiconductor element, wherein the cured film is the cured relief pattern according to [12].

  [14] A display device comprising a display element and a cured film provided on the display element, wherein the cured film is the cured relief pattern according to [12]. apparatus.

  According to the present invention, a photosensitive resin composition that is excellent in wet spreadability at the time of preparing a coating film by a spin coating method with a smaller discharge mass, and excellent in-plane uniformity of the coating film, the photosensitive resin composition Can be provided.

  Hereinafter, exemplary modes for carrying out the present invention (hereinafter abbreviated as “embodiments”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

<Photosensitive resin composition>
Each component which comprises the photosensitive resin composition of this invention is demonstrated concretely below.

(A) Alkali-soluble resin (A) Alkali-soluble resin used for this composition is resin which has acidic functional groups, such as a phenolic hydroxyl group and a carboxyl group, and is soluble in alkaline aqueous solution.

  Specifically, (A) the alkali-soluble resin includes (i) a hydroxypolyamide which is a PBO precursor, (ii) a polyamide derived from tetracarboxylic acid and a diamine and having a carboxyl group at the ortho position of the amide bond, (iii) ) Alkaline aqueous solution-soluble polyimide having a phenolic hydroxyl group in the side chain, (iv) Phenol resin and its derivative, (v) Polyhydroxystyrene and its derivative, (vi) Acrylic resin and its derivative, and these resins in the molecule It is a resin having a structure copolymerized. These resins may be used alone or in combination.

｛式中、Ｘ_１及びＹ_１は、各々独立に、２〜６０個の炭素原子を有する２〜８価の有機基を表し、Ｒ_１０及びＲ_１１は、各々独立に、水素原子又は炭素原子数１〜１０のアルキル基を表し、ｍ１は、１〜１０００の整数であり、ｎ１〜ｎ４は、それぞれ独立に、０〜４の整数であり、ｎ１及びｎ３は、０≦（ｎ１＋ｎ３）≦６を満たし、ｎ２及びｎ４は、０≦（ｎ２＋ｎ４）≦６を満たし、そしてｎ１〜ｎ４の全てが０になることはない。｝
で表される樹脂を主成分とする（ｉ）ＰＢＯ前駆体であるヒドロキシポリアミドが望ましい。
これは、ポリマーが処理後に環構造を有することで、耐熱性及び耐溶剤性が飛躍的に向上し、強靭な膜が得られるためである。 (A) The alkali-soluble resin is a polymer having an imide ring, an oxazole ring, or the like after heating or treatment with an appropriate catalyst, the following general formula (6):

{Wherein, X ₁ and Y ₁ each independently represent a 2 to 8 valent organic group having 2 to 60 carbon atoms, and R ₁₀ and R ₁₁ each independently represent a hydrogen atom or a carbon atom. Represents an alkyl group of formulas 1 to 10, m1 is an integer of 1 to 1000, n1 to n4 are each independently an integer of 0 to 4, and n1 and n3 are 0 ≦ (n1 + n3) ≦ 6. N2 and n4 satisfy 0 ≦ (n2 + n4) ≦ 6, and n1 to n4 do not all become zero. }
(I) Hydroxypolyamide, which is a PBO precursor, is preferable.
This is because when the polymer has a ring structure after the treatment, the heat resistance and the solvent resistance are remarkably improved, and a tough film is obtained.

  The resin structure in the alkali-soluble resin represented by the general formula (6) may be one type or two or more types. When two or more types of structural units are present, the arrangement of the structural units may be a block or random, and the repeat number m1 is the total number of repeats of the two or more types of structural units.

Hereinafter, (i) polyhydroxyamide which is a PBO precursor will be described in detail.
The repeating unit represented by the general formula (6) includes, for example, a dicarboxylic acid having a structure of Y ₁ (OH) _n2 (COOR ₁₁ ) _n4 (COOH) ₂ , and X ₁ (NH ₂ ) ₂ (OH) _n1 ( COOR ₁₀ ) It can be obtained by polycondensation of a diamine having an _n3 structure, such as bisaminophenol.
Since the two amino groups and hydroxy groups of the bisaminophenol are in the ortho positions with each other, the polyhydroxyamide is closed by heating to about 280 ° C. to 400 ° C. to form PBO which is a heat resistant resin. Change. m ₁ is preferably in the range of ₁ to 1000, preferably in the range of 1 to 300, more preferably in the range of 3 to 50, and most preferably in the range of 3 to 30.

Examples of the diamine having a X ₁ (NH ₂ ) ₂ (OH) _n1 (COOR ₁₀ ) _n3 structure include a bisaminophenol compound, specifically, 3,3′-dihydroxybenzidine, 3,3 ′. -Diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-diamino-3 , 3'-dihydroxydiphenylsulfone, bis- (3-amino-4-hydroxyphenyl) methane, 2,2-bis- (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino -4-hydroxyphenyl) hexafluoropropane, 2,2-bis- (4-amino-3-hydroxyphenyl) hexafluoropropane, bis- (4-amino-3-hydroxyphenyl) methane, 2,2-bis- (4-amino-3-hydroxyphenyl) propane, 4,4′-diamino-3,3′-dihydroxybenzophenone, 3,3′- Diamino-4,4′-dihydroxybenzophenone, 4,4′-diamino-3,3′-dihydroxydiphenyl ether, 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 1,4-diamino-2,5- Examples include dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, and 1,3-diamino-4,6-dihydroxybenzene. These bisaminophenol compounds may be used alone or in combination.

Among the diamines having the X ₁ (NH ₂ ) ₂ (OH) _n1 (COOR ₁₀ ) _n3 structure, particularly preferred is the case where X ₁ is an organic group selected from the following structures.

（式中、Ｘ₂は、少なくとも２個の炭素原子を有する４価の有機基である。）
上記Ｘ_２は、前述したＸ_１で示される有機基として好ましいものから成る群から選択される少なくとも１つの有機基であることが好ましい。 In addition, as a diamine having an X ₁ (NH ₂ ) ₂ (OH) _n1 (COOR ₁₀ ) _n3 structure, two sets of diamines having an amide bond and a phenolic hydroxyl group in the ortho position relative to each other (hereinafter referred to as “intramolecular It is also possible to use a diamine having a PBO precursor structure. Examples thereof include diamines represented by the following general formula, which are obtained by reacting the above-described bisaminophenol with two molecules of nitrobenzoic acid, followed by reduction.

(In the formula, X ₂ is a tetravalent organic group having at least 2 carbon atoms.)
X ₂ is preferably at least one organic group selected from the group consisting of those preferable as the organic group represented by X ₁ described above.

｛式中、Ｙ_２は、少なくとも２個の炭素原子を有する２価の有機基である。｝
上記Ｙ_２は、後述するＹ_１で示される有機基として好ましいものから成る群から選択される少なくとも１つの有機基であることが好ましい。 As another method for obtaining a diamine having a PBO precursor structure in the molecule, the dicarboxylic acid dichloride having the structure of Y ₂ (COCl) ₂ is reacted with two molecules of nitroaminophenol and reduced. There is also a method for obtaining a diamine.

{Wherein Y ₂ is a divalent organic group having at least two carbon atoms. }
Y ₂ is preferably at least one organic group selected from the group consisting of preferable organic groups represented by Y ₁ described later.

｛式中、Ｙ_３は、少なくとも４個の炭素原子を有する４価の有機基であり、そしてＲ_１２は、炭素原子数１〜１０の炭化水素基を表す。｝ In addition, as a bisaminophenol having an X ₁ (NH ₂ ) ₂ (OH) _n1 (COOR ₁₀ ) _n3 structure, a diamine having two polyimide precursor structures in the molecule (hereinafter referred to as “PI precursor structure in the molecule”). Can also be used. As a method for obtaining such a bisaminophenol compound, for example, dicarboxylic acid obtained by ring-opening tetracarboxylic dianhydride with monoalcohol or monoamine, and aniline having a hydroxy group and a nitro group at the ortho positions of each other are used. There is also a method of obtaining bisaminophenol represented by the following general formula by condensing two molecules and then reducing the nitro group.

{Wherein Y ₃ is a tetravalent organic group having at least 4 carbon atoms, and R ₁₂ represents a hydrocarbon group having 1 to 10 carbon atoms. }

In the resin represented by the general formula (6), a diamine that does not contain a phenolic hydroxyl group is used as a diamine, in addition to a diamine having a X ₁ (NH ₂ ) ₂ (OH) _n1 (COOR ₁₀ ) _n3 structure. You can also. Examples of such diamines include aromatic diamines, aliphatic diamines, and silicon diamines.

  Examples of the aromatic diamine include m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl ketone, 4,4′-diaminodiphenyl ketone, 3,4′-diaminodiphenyl ketone, 2,2′-bis (4-aminophenyl) propane 2,2′-bis (4-aminophen L) Hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4-methyl-2 , 4-bis (4-aminophenyl) -1-pentene, 4-methyl-2,4-bis (4-aminophenyl) -2-pentene, 1,4-bis (α, α-dimethyl-4-amino) Benzyl) benzene, imino-di-p-phenylenediamine, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 4-methyl-2,4-bis (4-aminophenyl) pentane, 5 (or 6)- Amino-1- (4-aminophenyl) -1,3,3-trimethylindane, bis (p-aminophenyl) phosphine oxide, 4,4′-diaminoazobenzene, 4, '-Diaminodiphenylurea, 4,4'-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-amino) Phenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] benzophenone, 4,4′-bis (4-aminophenoxy) diphenylsulfone, 4,4′-bis [4- (Α, α-dimethyl-4-aminobenzyl) phenoxy] benzophenone, 4,4′-bis [4- (α, α-dimethyl-4-aminobenzyl) phenoxy] diphenylsulfone, 4,4′-diaminobiphenyl, 4,4′-diaminobenzophenone, phenylindanediamine, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3, 3'-dimethyl-4,4'-diaminobiphenyl, o-toluidine sulfone, 2,2-bis (4-aminophenoxyphenyl) propane, bis (4-aminophenoxyphenyl) sulfone, bis (4-aminophenoxyphenyl) Sulfide, 1,4- (4-aminophenoxyphenyl) benzene, 1,3- (4-aminophenoxyphenyl) benzene, 9,9-bis (4-aminophenyl) fluorene, 4,4′-di- (3 -Aminophenoxy) diphenylsulfone, 4,4'-diaminobenzanilide and the like, and the hydrogen atom of the aromatic nucleus of these aromatic diamines is a chlorine atom, a fluorine atom, a bromine atom, a methyl group, a methoxy group, a cyano group, and And compounds substituted by at least one group or atom selected from the group consisting of phenyl groups. .

  Examples of the aliphatic diamine include 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, , 12-dodecanediamine and the like; 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, Branched chain aliphatic diamines such as 2,4,4-trimethyl-1,6-hexanediamine, 2-methyl-1,8-octanediamine, 5-methyl-1,9-nonanediamine; cyclohexanediamine, methylcyclohexanediamine , Isophoronediamine, bis (4-aminocyclohexyl) methane, norbornanedimethylamine, trisic And alicyclic diamines such as lodecane dimethylamine.

  Examples of the silicon diamine include bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, bis (4-aminophenyl) tetramethyldisiloxane, and bis (γ-aminopropyl) tetramethyldi Examples include siloxane, 1,4-bis (γ-aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, and bis (γ-aminopropyl) tetraphenyldisiloxane.

｛式中、Ａ₁は、−ＣＨ₂−、−Ｏ−、−Ｓ−、−ＳＯ₂−、−ＣＯ−、−ＮＨＣＯ−及び−Ｃ（ＣＦ_３）₂−から成る群から選択される少なくとも１つの２価の基又は単結合であり、ｍ₂は、１〜３０の整数であり、Ｌ₁は、それぞれ独立に、炭素数１〜４のアルキル基、不飽和基、及びハロゲン原子から成る群から選択される少なくとも１つの基であり、ｊは、それぞれ独立に、０〜４の整数であり、ｋは、０又は１の整数であり、そしてｌは、０〜２の整数である。｝ The dicarboxylic acid having _{Y 1 (OH) n2 (COOR} 11) n4 (COOH) 2 structure, selected from the _{structures Y 1} is represented by the following formula, an aromatic group, an alicyclic group, or an aliphatic group The dicarboxylic acid which is is mentioned.

{Wherein A ₁ is at least selected from the group consisting of —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO— and —C (CF ₃ ) ₂ —. One divalent group or a single bond, m ₂ is an integer of 1 to 30, and each L ₁ independently comprises an alkyl group having 1 to 4 carbon atoms, an unsaturated group, and a halogen atom. At least one group selected from the group, j is each independently an integer of 0-4, k is an integer of 0 or 1, and l is an integer of 0-2. }

  Examples of the aromatic dicarboxylic acid include isophthalic acid, terephthalic acid, 2,2-bis (4-carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, and 4,4′-dicarboxy. Biphenyl, 4,4′-dicarboxydiphenyl ether, 4,4′-dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2,2-bis (p-carboxyphenyl) propane, 5-tert-butylisophthal Examples include acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, and 2,6-naphthalenedicarboxylic acid.

  Examples of the alicyclic dicarboxylic acid include 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, hexahydrophthalic acid, and tetrahydrophthalic acid.

  Examples of the aliphatic dicarboxylic acid include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, and 2,2-dimethylsuccinic acid. Siric acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3- Dimethyl glutaric acid, 3-ethyl-3-methyl glutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluoro Suberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanedioic acid, dode Diacid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosandioic acid, heneicosandioic acid, docosandioic acid, tricosanedioic acid, tetracosandioic acid Examples include acids, pentacosane diacids, hexacosane diacids, heptacosane diacids, octacosane diacids, nonacosane diacids, triacontane diacids, hentriacontan diacids, dotriacontane diacids, diglycolic acid and the like.

Alternatively, a derivative of 5-aminoisophthalic acid may be used for a part or all of the dicarboxylic acid having the Y ₁ (OH) _n2 (COOR ₁₁ ) _n4 (COOH) ₂ structure.
Specific compounds to be reacted with 5-aminoisophthalic acid to obtain the derivative include 5-norbornene-2,3-dicarboxylic acid anhydride, exo-3,6-epoxy-1,2,3, 6-tetrahydrophthalic anhydride, 3-ethynyl-1,2-phthalic anhydride, 4-ethynyl-1,2-phthalic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, 1 -Cyclohexene-1,2-dicarboxylic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, allyl succinic anhydride , Isocyanate ethyl methacrylate, 3-isopropenyl-α, α-dimethylbenzyl isocyanate 3-cyclohexene-1-carboxylic acid chloride, 2-furancarboxylic acid chloride, crotonic acid chloride, cinnamic acid chloride, methacrylic acid chloride, acrylic acid chloride, propiolic acid chloride, tetrolic acid chloride, thiophene-2-acetyl chloride, p-styrene sulfonyl chloride, glycidyl methacrylate, allyl glycidyl ether, chloroformate methyl ester, chloroformate ethyl ester, chloroformate n-propyl ester, chloroformate isopropyl ester, chloroformate isobutyl ester, chloroformate 2- Ethoxy ester, chloroformate-sec-butyl ester, chloroformate benzyl ester, chloroformate 2-ethylhexyl ester, chloroformate allyl ester, chloroformate phenyl ester, chloroformate 2,2,2-trichloroethyl ester, chloroformate-2-butoxyethyl ester, chloroformate-p-nitrobenzyl ester, chloroformate-p-methoxybenzyl ester, chloroformate isobornylbenzyl ester, chloro Formic acid-p-biphenylisopropylbenzyl ester, 2-t-butyloxycarbonyl-oxyimino-2-phenylacetonitrile, St-butyloxycarbonyl-4,6-dimethyl-thiopyrimidine, di-tert-butyl-dicarbonate N-ethoxycarbonylphthalimide, ethyldithiocarbonyl chloride, formic acid chloride, benzoyl chloride, p-toluenesulfonic acid chloride, methanesulfonic acid chloride, acetyl chloride, trityl chloride, trimethylchlorosilane, hexamethyldisilazaza N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) trifluoroacetamide, (N, N-dimethylamino) trimethylsilane, (dimethylamino) trimethylsilane, trimethylsilyldiphenylurea, bis (trimethylsilyl) urea, phenyl isocyanate N-butyl isocyanate, n-octadecyl isocyanate, o-tolyl isocyanate, 1,2-phthalic anhydride, and cis-1,2-cyclohexanedicarboxylic anhydride, and glutaric anhydride.

｛式中、Ｂは、−ＣＨ₂−、−Ｏ−、−Ｓ−、−ＳＯ₂−、−ＣＯ−、−ＮＨＣＯ−、及び−Ｃ（ＣＦ_３）₂−、−ＣＯＯ−から成る群から選択される少なくとも１つの２価の基を表す。｝ Furthermore, as a dicarboxylic acid having a Y ₁ (OH) _n2 (COOR ₁₁ ) _n4 (COOH) ₂ structure, a dicarboxylic acid obtained by ring-opening a tetracarboxylic dianhydride with a monoalcohol, a monoamine or the like can be used. Here, examples of monoalcohol include methanol, ethanol, propanol, isopropanol, butanol, t-butanol, benzyl alcohol and the like. Examples of monoamines include butylamine and aniline. As an example of said tetracarboxylic dianhydride, the compound shown by following Chemical formula is mentioned.

{Wherein B is selected from the group consisting of —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, and —C (CF ₃ ) ₂ —, —COO—. Represents at least one divalent group selected. }

  Alternatively, tetracarboxylic dianhydride can be reacted with bisaminophenol or diamine, and the resulting carboxylic acid residue can be esterified or amidated with a monoalcohol or monoamine.

｛式中、Ｘ_３は、前述のＸ_１（ＯＨ）₂（ＮＨ−）₂で表される２価の有機基を表す。｝ Also, trimellitic acid chloride is reacted with bisaminophenol to produce tetracarboxylic dianhydride, and ring-opened in the same manner as the above tetracarboxylic dianhydride and used as dicarboxylic acid You can also. Examples of the tetracarboxylic dianhydride thus obtained include chemical formulas represented by the following chemical formulas.

{Wherein X ₃ represents a divalent organic group represented by the aforementioned X ₁ (OH) ₂ (NH—) ₂ . }

  As a method of polycondensation of the dicarboxylic acid and bisaminophenol compound or diamine for synthesizing polyhydroxyamide, dicarboxylic acid and thionyl chloride are used to form dicarboxylic acid chloride and then bisaminophenol or diamine is allowed to act. And a method of polycondensation of dicarboxylic acid and bisaminophenol or diamine with dicyclohexylcarbodiimide. In the method using dicyclohexylcarbodiimide, hydroxybenztriazole can be allowed to act simultaneously.

  In the polyhydroxyamide having a repeating unit represented by the above general formula (6), it is also preferable to use the end group sealed with an organic group (hereinafter referred to as “sealing group”).

  For example, in the polycondensation of hydroxypolyamide, when the dicarboxylic acid component is used in an excess number of moles compared to the sum of the bisaminophenol component and the diamine component, a compound having an amino group or a hydroxyl group is used as a sealing group. Is preferred. Examples of the compound include aniline, ethynylaniline, norborneneamine, butylamine, propargylamine, ethanol, propargyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, and hydroxyethyl acrylate.

  Conversely, when the sum of the bisaminophenol component and the diamine component is used as an excess number of moles compared to the dicarboxylic acid component, as the compound having a blocking group, an acid anhydride, carboxylic acid, acid chloride, or It is preferable to use a compound having an isocyanate group or the like. Examples of the compound include benzoyl chloride, norbornene dicarboxylic anhydride, norbornene carboxylic acid, ethynyl phthalic anhydride, glutaric anhydride, maleic anhydride, phthalic anhydride, cyclohexane dicarboxylic anhydride, methylcyclohexane dicarboxylic anhydride Products, cyclohexene dicarboxylic acid anhydride, methacryloyloxyethyl methacrylate, phenyl isocyanate, mesyl chloride, tosyl chloride and the like.

｛式中、Ｌ_２は、−ＣＨ₂−、−Ｏ−又は−Ｓ−を表し、そしてＬ_３は、水素原子、炭素原子数１〜６のアルキル基又は炭素原子数２〜６のアルケニル基を表す。｝
で表される基が挙げられる。 Among these, preferred end groups include the following structures:

{Wherein L ₂ represents —CH ₂ —, —O— or —S—, and L ₃ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms. Represents. }
The group represented by these is mentioned.

  (Ii) A polyamide derived from tetracarboxylic dianhydride and a diamine and having a carboxyl group at the ortho position of the amide bond is obtained by converting the above-described tetracarboxylic dianhydride and the above-mentioned diamine having no phenolic hydroxyl group to γ -Obtained by a condensation reaction in a polar organic solvent such as butyrolactone, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, tetramethylurea, or sulfolane, using a catalyst such as pyridine or triethylamine as necessary. .

  The average weight molecular weight of the polyamide is preferably in the range of 8000-70000. As a method for adjusting the molecular weight, a method of controlling by changing the molar ratio of the charged tetracarboxylic acid and diamine can be used. A method in which tetracarboxylic acid is added more than diamine to obtain a carboxylic acid terminal is preferable from the viewpoint of storage stability at room temperature. Moreover, after charging diamine more than tetracarboxylic acid, a terminal group can also be sealed and used with the compound which has an acid anhydride, carboxylic acid, acid chloride, an isocyanate group, etc.

  The polyamide resin containing the solvent obtained by the above reaction can be used as a resin composition as it is, and the polycondensate is obtained through a purification step without using the produced polycondensate solution as it is. May be isolated and redissolved in a suitable solvent before use. As a specific purification step, first, a polycondensate is precipitated by adding a poor solvent such as methanol, ethanol, isopropanol, or water to the polycondensate solution obtained by the above production method. Next, it is dissolved again in a good solvent such as γ-butyrolactone and N-methylpyrrolidone, and the solution is passed through a column packed with an ion exchange resin to remove ionic impurities. Finally, it is a purification step in which the solution is dropped into pure water, the precipitate is filtered off, and vacuum dried. Thereby, a low molecular weight component, an ionic impurity, etc. can also be removed.

(Iii) An aqueous alkaline solution-soluble polyimide having a phenolic hydroxyl group in the side chain comprises the tetracarboxylic acid anhydride and the diamine having the X ₁ (NH ₂ ) ₂ (OH) _n1 (COOR ₁₀ ) _n3 structure, γ -In a polar organic solvent such as butyrolactone, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, tetramethylurea, sulfolane, and the like, using a catalyst such as pyridine or triethylamine, if necessary, a condensation reaction is carried out to obtain a polyimide precursor. Subsequently, it is obtained by dehydrating and ring-closing the polyimide precursor by heating in the presence or absence of a catalyst such as pyridine and acetic anhydride.
The average weight molecular weight of the polyimide resin is preferably in the range of 5000 to 70000. As a method of adjusting the molecular weight, a method of controlling by changing the charged molar ratio of tetracarboxylic acid and diamine can be used. In view of storage stability at room temperature, a method in which tetracarboxylic acid is charged more than diamine to obtain a carboxylic acid terminal is preferable. It is also possible to charge diamine more than acid anhydride and use it with the terminal group sealed with a compound having acid anhydride, carboxylic acid, acid chloride, isocyanate group or the like.
The polyamide resin containing the solvent obtained by the above reaction can be used as it is as a resin composition, or may be subjected to a purification step as described above.

(A) As an alkali-soluble resin, (iv) a phenol resin and derivatives thereof are also preferably used.
(A) When a phenol resin is used as the alkali-soluble resin, (B) the affinity with the photoacid generator is high, so that the unexposed part has a dissolution inhibiting effect, while the exposed part has a dissolution promoting action. A high contrast and high resolution photosensitive resin composition can be obtained by generating a high contrast.
In addition, when the photosensitive resin composition is spin-coated, exposed, developed, and cured on a metal and then etched using a fluorine-based compound gas, the fluorine-based compound gas used for the etching is a phenolic resin during the etching process. Since it does not easily penetrate into the cured film, corrosion due to the fluorine-based compound hardly occurs on the metal.
Furthermore, since the phenol resin has high affinity for organic solvents and high solubility, the in-plane uniformity tends to be excellent when spin coating is performed, and the film thickness at the edge of the substrate tends to be uniform.

  The above effect is derived not only when the phenol resin alone is used as the alkali-soluble resin, but also from the phenol resin and the above-mentioned (i) polyhydroxyamide which is a PBO precursor, (ii) tetracarboxylic acid and diamine, It is also manifested when a polyamide having a carboxyl group at the ortho position of the amide bond and (iii) an alkaline aqueous solution-soluble polyimide having a phenolic hydroxyl group in the side chain are mixed.

  When 100 parts by mass of the polymers (i) to (iii) are mixed with 10 parts by mass to 300 parts by mass, preferably 50 parts by mass to 150 parts by mass, the phenol resin becomes highly sensitive to electron beams. Therefore, it is preferably 300 parts by mass or less from the viewpoint of heat resistance.

  As a method for synthesizing a phenol resin, one of various phenol compounds or an arbitrary mixture thereof is polycondensed with aldehydes such as formalin by a known method, or a phenol compound, a methylol group, an alkoxymethyl group, and Examples thereof include a method of synthesizing a compound having two haloalkyl groups in the molecule by a polymerization reaction under an acid catalyst, or a method of synthesizing them.

  Examples of phenols include phenol, orthocresol, metacresol, paracresol, 2,3-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,4- Dimethylphenol, 2,6-dimethylphenol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, 2-t-butylphenol, 3-t-butylphenol, 4-t-butylphenol, 2-methylresorcinol 4-methylresorcinol, 5-methylresorcinol, 4-t-butylcatechol, 2-methoxyphenol, 3-methoxyphenol, 2-propylphenol, 3-propylphenol, 4-propylphenol, 2-isopropylphenol, 2- Meto Shi-5-methylphenol, 2-t-butyl-5-methylphenol, thymol, and the like Isochimoru. These can be used alone or in combination of two or more.

  Examples of aldehydes include formaldehyde, formalin, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropionaldehyde, β-phenylpropionaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p- Hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, terephthalaldehyde, etc. It is done.

  Examples of ketones include acetone, methyl ethyl ketone, diethyl ketone, and diphenyl ketone. These can be used alone or in combination of two or more.

  Examples of the compound having two methylol groups in the molecule include bis (hydroxymethyl) cresol, 2,6-bis (hydroxymethyl) -4-ethylphenol, and 2,6-bis (hydroxymethyl) -4- Propylphenol, 2,6-bis (hydroxymethyl) -4-n-butylphenol, 2,6-bis (hydroxymethyl) -4-t-butylphenol, 2,6-bis (hydroxymethyl) -4-methoxyphenol, 2,6-bis (hydroxymethyl) -4-ethoxyphenol, 2,6-bis (hydroxymethyl) -4-propoxyphenol, 2,6-bis (hydroxymethyl) -4-n-butoxyphenol, 2,6 -Bis (hydroxymethyl) -4-t-butoxyphenol, bis (hydroxymethyl) biphenyl, etc. And the like.

  Examples of the compound having two alkoxymethyl groups in the molecule include bis (methoxymethyl) cresol, 2,6-bis (methoxymethyl) -4-ethylphenol, and 2,6-bis (methoxymethyl) -4. -Propylphenol, 2,6-bis (methoxymethyl) -4-n-butylphenol, 2,6-bis (methoxymethyl) -4-tert-butylphenol, 2,6-bis (methoxymethyl) -4-methoxyphenol 2,6-bis (methoxymethyl) -4-ethoxyphenol, 2,6-bis (methoxymethyl) -4-propoxyphenol, 2,6-bis (methoxymethyl) -4-n-butoxyphenol, 2, Examples include 6-bis (methoxymethyl) -4-t-butoxyphenol and bis (methoxymethyl) biphenyl. The number of carbon atoms of the alkoxymethyl group is preferably 1 to 10, more preferably 1 to 2, and most preferably 1 from the viewpoint of reaction activity.

  Examples of the compound having two haloalkyl groups in the molecule include bischloromethylbiphenyl and the like.

  The weight average molecular weight of the phenol resin is preferably 1,000 to 50,000, more preferably 2,000 to 20,000. The weight average molecular weight is preferably 1,000 or more from the viewpoint of elongation, and preferably 50,000 or less from the viewpoint of alkali solubility. In the present specification, the weight average molecular weight is a value obtained in terms of standard polystyrene using gel permeation chromatography (GPC).

  (V) The polyhydroxystyrene resin and derivatives thereof will be described in detail. Specific examples of the polyhydroxystyrene resin and derivatives thereof include, for example, poly-o-hydroxystyrene, poly-m-hydroxystyrene, poly-p-hydroxystyrene, poly-α-methyl-o-hydroxystyrene, poly-α. -Methyl-m-hydroxystyrene, poly- [alpha] -methyl-p-hydroxystyrene, or a partially acetylated product, a silylated product thereof or the like. The mass average molecular weight of these polyhydroxystyrene resins or derivatives thereof is usually in the range of 3,000 to 100,000, particularly preferably 4,000 to 20,000.

  (Iv) As acrylic resins and derivatives thereof, for example, acrylic acid, methacrylic acid, maleic acid, and their derivatives, which are monomers having an alkali-soluble group, are used in the presence of an anionic polymerization initiator or a cationic polymerization initiator. An acrylic resin obtained by polymerization can be used. In addition, these alkali-soluble monomers and alkali-insoluble acrylic acid esters, methacrylic acid esters, maleic acid esters, styrene, vinyl alcohol, vinyl acetate, vinyl esters, and derivatives thereof have a water-soluble range. May be copolymerized. The weight average molecular weight of the acrylic resin or its derivative is usually in the range of 3,000 to 100,000, particularly preferably 4,000 to 20,000.

(B) Photoacid generator As the photoacid generator (B) contained in the photosensitive resin composition of the present invention, the photosensitive resin composition can be applied to a desired application in a positive type or a negative type. Can be used. When the photosensitive resin composition is used as a positive type, as the photoacid generator (B), for example, a quinonediazide compound, an onium salt, a halogen-containing compound, and the like can be used. From the viewpoint of properties, a quinonediazide compound is preferable.

  Examples of the onium salt include iodonium salts, sulfonium salts, phosphonium salts, ammonium salts, diazonium salts, and the like, and onium salts selected from the group consisting of diaryliodonium salts, triarylsulfonium salts, and trialkylsulfonium salts. Is preferred.

  Examples of the halogen-containing compound include a haloalkyl group-containing hydrocarbon compound, and trichloromethyltriazine is preferable from the viewpoint of increasing sensitivity.

  As the quinonediazide compound, a naphthoquinonediazide compound (hereinafter also referred to as “NQD compound”) is preferable, and a compound having a 1,2-naphthoquinonediazide structure is particularly preferable. The naphthoquinonediazide structure includes 1,2-naphthoquinonediazide-4-sulfonic acid ester of a polyhydroxy compound having a specific structure described in detail below, and 1,2-naphthoquinonediazide-5-sulfonic acid ester of the polyhydroxy compound. At least one NQD compound selected from the group consisting of:

  The NQD compound is obtained by subjecting a naphthoquinone diazide sulfonic acid compound to sulfonyl chloride with chlorosulfonic acid or thionyl chloride according to a conventional method, and subjecting the obtained naphthoquinone diazide sulfonyl chloride to a polyhydroxy compound. For example, a polyhydroxy compound and a predetermined amount of 1,2-naphthoquinonediazide-5-sulfonyl chloride or 1,2-naphthoquinonediazide-4-sulfonyl chloride in a solvent such as dioxane, acetone, tetrahydrofuran, etc. The NQD compound can be obtained by reacting in the presence of a basic catalyst for esterification, and washing the resulting product with water and drying.

｛式中、Ｑは、水素原子、又は下記式群のいずれかで表されるナフトキノンジアジドスルホン酸エステル基であるが、全てのＱが水素原子であることはない。｝

Examples of preferable NQD compounds include those represented by the following general formula group.

{In the formula, Q is a hydrogen atom or a naphthoquinonediazide sulfonate group represented by any of the following formula groups, but not all Qs are hydrogen atoms. }

  In addition, as the NQD compound, a naphthoquinone diazide sulfonyl ester compound containing a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule can be used, or a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphtho quinone. It can also be used by mixing with a quinonediazide sulfonyl ester compound.

  When used as a positive photosensitive resin composition, the blending amount of the (B) photoacid generator with respect to the whole (A) alkali-soluble resin is 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the total alkali-soluble resin. Is preferable, and 5 to 30 parts by mass is more preferable. (B) When the compounding quantity of a photo-acid generator is 1 mass part or more, the patterning property of resin is favorable, and on the other hand, the tensile elongation rate of the film | membrane after hardening is favorable in it being 50 mass parts or less. Moreover, it is preferable because there is little development residue (scum) in the exposed area.

  The photosensitive resin composition of the present invention is a negative photosensitive resin composition by combining (B) a photoacid generator of (A) to (K) below with a (D) crosslinking agent described later. Available. In this case, examples of the (B) photoacid generator include the following compounds.

A) Trichloromethyl-s-triazines Tris (2,4,6-trichloromethyl) -s-triazine, 2-phenyl-bis (4,6-trichloromethyl) -s-triazine, 2- (3-chlorophenyl) -Bis (4,6-trichloromethyl) -s-triazine, 2- (2-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -bis (4 6-trichloromethyl) -s-triazine, 2- (3-methoxyphenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methoxyphenyl) -bis (4,6-trichloromethyl) ) -S-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3-methylthiophenyl) Bis (4,6-trichloromethyl-s-triazine, 2- (2-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -bis (4,6 -Trichloromethyl) -s-triazine, 2- (3-methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methoxynaphthyl) -bis (4,6-trichloromethyl) -S-triazine, 2- (3,4,5-trimethoxy-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methylthio-β-styryl) -bis (4 , 6-Trichloromethyl) -s-triazine, 2- (3-methylthio-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methylthio-β Styryl) - bis (4,6-trichloromethyl) -s-triazine.

A) Diaryliodonium diphenyliodonium tetrafluoroborate, diphenyliodonium tetrafluorophosphate, diphenyliodonium tetrafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, 4-methoxyphenyl Phenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenylphenyliodonium hexafluoroarsenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, 4- Meto Xiphenylphenyliodonium-p-toluenesulfonate, bis (4-ter-butylphenyl) iodonium tetrafluoroborate, bis (4-ter-butylphenyl) iodonium hexafluoroarsenate, bis (4-ter-butylphenyl) iodonium Trifluoromethanesulfonate, bis (4-ter-butylphenyl) iodonium trifluoroacetate, bis (4-ter-butylphenyl) iodonium-p-toluenesulfonate, and the like.

C) Triarylsulfonium salts Triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfo NATO, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium methanesulfonate, 4-methoxyphenyldiphenylsulfonium tri Fluoroacetate, 4- Methoxyphenyldiphenylsulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate, 4-phenylthiophenyldiphenylhexafluoroarsenate, 4-phenylthiophenyldiphenyltrifluoromethane Sulfonate, 4-phenylthiophenyl diphenyl trifluoroacetate, 4-phenylthiophenyl diphenyl-p-toluene sulfonate and the like.

  Among these compounds, trichloromethyl-S-triazines include 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -S-triazine, 2- (4-chlorophenyl) -bis (4, 6-trichloromethyl) -S-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -S-triazine, 2- (4-methoxy-β-styryl) -bis (4,6 -Trichloromethyl) -S-triazine, 2- (4-methoxynaphthyl) -bis (4,6-trichloromethyl) -S-triazine, and the like as diaryliodonium salts include diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethane. Sulfonate, 4-methoxyphenylphenyliodonium trifluoromethane For example, sulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, and triarylsulfonium salts include triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium methanesulfonate, 4-methoxyphenyldiphenyl. Suitable examples include sulfonium trifluoroacetate, 4-phenylthiophenyl diphenyl trifluoromethanesulfonate, 4-phenylthiophenyl diphenyl trifluoroacetate, and the like.

D) Diazoketone compound Examples of the diazoketone compound include 1,3-diketo-2-diazo compound, diazobenzoquinone compound, diazonaphthoquinone compound, and the like, and specific examples include 1,2-naphthoquinonediazide-4 of phenols. -A sulfonic acid ester compound can be mentioned.

E) Sulfone compounds Examples of the sulfone compounds include β-ketosulfone compounds, β-sulfonylsulfone compounds and α-diazo compounds of these compounds. Specific examples include 4-trisphenacylsulfone, mesitylphenacyl. Examples include sulfone and bis (phenacylsulfonyl) methane.

F) Sulfonic acid compound Examples of the sulfonic acid compound include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates. Preferred examples include benzoin tosylate, pyrogallol tris trifluoromethane sulfonate, o-nitrobenzyl trifluoromethane sulfonate, o-nitrobenzyl p-toluene sulfonate, and the like.

G) Sulfonimide compound Specific examples of the sulfonimide compound include, for example, N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N -(Trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide and the like can be mentioned.

C) Oxime ester compound 2- [2- (4-Methylphenylsulfonyloxyimino)]-2,3-dihydrothiophene-3-ylidene] -2- (2-methylphenyl) acetonitrile (trade name “Ciba Specialty Chemicals”) "Irgacure PAG121"), [2- (propylsulfonyloxyimino) -2,3-dihydrothiophene-3-ylidene] -2- (2-methylphenyl) acetonitrile (Ciba Specialty Chemicals trade name "Irgacure PAG103"), [ 2- (n-octanesulfonyloxyimino) -2,3-dihydrothiophene-3-ylidene] -2- (2-methylphenyl) acetonitrile (Ciba Specialty Chemicals trade name “Irgacure PAG108”), α- (n- Octanesulfonyloxy Imino) -4-methoxybenzyl cyanide (Ciba Specialty Chemicals tradename "CGI725"), and the like.

I) Diazomethane compounds Specific examples of the diazomethane compounds include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, and the like.

  In particular, from the viewpoint of sensitivity, the oxime ester compound group is particularly preferable.

  (B) When a negative photosensitive resin composition is formed by combining a photoacid generator with (D) a crosslinking agent described later, the blending amount of (B) photoacid generator is 100 masses of the total alkali-soluble resin. Part to 0.1 part by mass with respect to part. If the blending amount is 0.1 parts by mass or more, a sensitivity improvement effect can be sufficiently obtained, and if the blending amount is 100 parts by mass or less, mechanical properties after curing are good. The blending amount is preferably 1 to 40 parts by mass.

(C) a 10Pa~250Pa vapor pressure at 25 ° C., and in the embodiment of the density solvent present invention is 0.7g ^/ cm ³ ~1.02g ^/ cm 3 at 25 ℃, (A) an alkali-soluble When the resin and (B) photoacid generator are dissolved in a solvent to form a varnish and used as a photosensitive resin composition for spin coating, (C) the vapor pressure at 25 ° C. is 10 Pa to 250 Pa and the density is 0. Use a solvent of 7 to 1.02 g / cm ³ .

If the density is a photosensitive resin composition containing a solvent of ^{0.7g / cm 3 ~1.02g / cm 3} , are widely used in the photosensitive resin composition γ--butyrolactone (density 1.13 g / cm Compared with the photosensitive resin composition comprised by ³ ), the density of the photosensitive resin composition becomes small. In the photosensitive resin composition having a high density and the photosensitive resin composition having a low density, when a varnish of the same mass is discharged onto a substrate to be spin-coated, the volume of the varnish is increased in the photosensitive resin composition having a low density. The present inventors have found that a wider area can be coated.
That is, when coating a silicon wafer or the like having a predetermined area on the substrate, if a photosensitive resin composition having a low density is used, the amount of varnish necessary for coating the entire surface is reduced.

  Further, by using a solvent having a vapor pressure at 25 ° C. of 10 Pa to 250 Pa, the uniformity of the coating film is dramatically improved. When a solvent with a vapor pressure of 10 Pa or more is used, the solvent component is sufficiently volatilized at the time of pre-baking, so the solvent is removed from the film after pre-baking, and the influence of uneven temperature or exhaust of the hot plate used during pre-baking is small. The film thickness uniformity of the coating film after pre-baking becomes good. Further, when a solvent having a vapor pressure of 10 Pa or more is used, the film thickness of the edge portion of the substrate becomes uniform after coating. On the other hand, when a solvent having a vapor pressure of 250 Pa or less is used, the solvent component becomes difficult to volatilize excessively at the time of spin coating, so the film thickness uniformity is improved.

(C) a pressure at 25 ° C. is 10Pa～250Pa, and as the solvent density at 25 ° C. is ^{0.7g / cm 3 ~1.02g / cm 3} , specifically, (A) an alkali-soluble resin From the viewpoint of solubility or density with respect to water, ketone, ether, alcohol, and glycol are preferred.

｛式中、Ｒ_１及びＲ_２は、それぞれ独立に、炭素原子数１〜９のアルキル基であり、そしてＲ_１とＲ_２の炭素原子数の和が、７〜１０である。｝ The ketone solvent preferably has a structure represented by the following general formula (1).

{In the formula, R ₁ and R ₂ are each independently an alkyl group having 1 to 9 carbon atoms, and the sum of the carbon atoms of R ₁ and R ₂ is 7 to 10. }

  Specific examples of the ketone solvent include diisobutyl ketone, 5-methyl-3-heptanone, 2-methyl-3-heptanone, 6-methyl-2-heptanone, 2-methyl-4-heptanone, 3-methyl- 4-heptanone, 2-octanone, 3-octanone, 4-octanone, 5-methyl-2-octanone, 2-nonanone, 3-nonanone, 4-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4- Examples include decanone, 5-decanone, propiophenone, 1-phenylacetone, 3,3-dimethylpentane-4,4-dione, and cyclooctanone.

  Among these, diisobutyl ketone, 2-octanone, 2-nonanone, and 2-decanone are excellent in in-plane uniformity of the coating film, and the density of the photosensitive resin composition is lowered, and when a coating film is prepared by a spin coating method. From the viewpoint that the discharge mass can be reduced, 2-octanone or 2-nonanone is most preferable.

｛式中、Ｒ_３及びＲ_４は、それぞれ独立に、炭素原子数１〜１１のアルキル基であり、そしてＲ_３とＲ_４の炭素原子数の和が、９〜１２である。｝ The ether solvent preferably has a structure represented by the following general formula (2).

{In the formula, R ₃ and R ₄ are each independently an alkyl group having 1 to 11 carbon atoms, and the sum of the number of carbon atoms of R ₃ and R ₄ is 9 to 12. }

  Specific examples of ether solvents include amyl ether, isoamyl ether, 1-ethoxyheptane, 1-propoxyheptane, 1-butoxyheptane, 1-propoxyheptane, 1-methoxyoctane, 1-ethoxyoctane, 1-propoxy. Examples include octane, 1-butoxyoctane, 1-methoxynonane, 1-ethoxynonane, 1-propoxynonane, benzyl methyl ether, and benzyl dimethyl ether.

  Among these, amyl ether, isoamyl ether, 1-methoxyoctane, and 1-butoxyoctane are preferable from the viewpoint of decreasing the density of the photosensitive resin composition and reducing the discharge mass at the time of preparing a coating film by a spin coating method. Ether is most preferred.

｛式中、Ｒ_５は、炭素原子数５〜１０のアルキル基である。｝ The alcohol solvent is preferably a structure represented by the following general formula (3).

{Wherein R ₅ is an alkyl group having 5 to 10 carbon atoms. }

  Specific examples of the alcohol solvent include 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, 1-octanol, 2-octanol, and 3-octanol. 4-octanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 4-methyl-1-pentanol, 2-methyl-1-hexanol, 3-methyl-1-hexanol, 4- Methyl-1-hexanol, 5-methyl-1-hexanol, 2-methyl-2-hexanol, 3-methyl-2-hexanol, 4-methyl-2-hexanol, 5-methyl-2-hexanol, 2-ethyl- 1-hexanol, cyclohexanol, cycloheptanol, cyclooctanol, etc. .

  Among these, 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, and 2-ethyl-1-hexanol are excellent in in-plane uniformity of the coating film, and the density of the photosensitive resin composition is lowered. From the viewpoint that the discharge mass at the time of preparing a coating film by spin coating can be reduced, 1-heptanol and 2-ethyl-1-hexanol are most preferable.

｛式中、Ｒ_６及びＲ_７は、それぞれ独立に、水素原子、炭素原子数１〜５のアルキル基、又は下記一般式（５）：

（式中、Ｒ_９は、炭素原子数１〜５のアルキル基を表す）
で表される基Ｘを表すが、Ｒ_６及びＲ_７の両方が基Ｘになることはなく、Ｒ_８は、水素原子又は炭素数１若しくは２のアルキル基を表し、そしてｎ５は、１≦ｎ５≦３を満たす数である。｝ As a glycol solvent, the structure represented by General formula (4) is preferable.

{In the formula, R ₆ and R ₇ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or the following general formula (5):

(Wherein R ₉ represents an alkyl group having 1 to 5 carbon atoms)
In which R ₆ and R ₇ are not both X, R ₈ represents a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, and n5 represents 1 ≦ It is a number satisfying n5 ≦ 3. }

  Specific examples of glycol solvents include propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono Examples include propyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol ethyl ether acetate, dipropylene glycol dimethyl ether, and dipropylene glycol methyl propyl ether. Among them, further, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol dimethyl ether, and dipropylene glycol methylpropyl ether are coated. It is preferable from the viewpoint of excellent in-plane uniformity of the film, the density of the photosensitive resin composition is lowered, and the discharge mass at the time of coating film preparation by spin coating can be reduced. Dipropylene glycol dimethyl ether and dipropylene glycol methyl Propyl ether is most preferred.

In the embodiment, in addition to the (C) solvent, density at 25 ° C. of spin coating the photosensitive resin composition does not exceed the range of ^{0.75g / cm 3 ~1.1g / cm 3} , and 25 ° C. In the range where the viscosity does not exceed 0.5 Pa · s to 2 Pa · s, for example, one or more of the following solvents can be mixed and used.
Examples of such a solvent include N-methyl-2-pyrrolidone, γ-butyrolactone (GBL), N, N-dimethylacetamide (hereinafter also referred to as “DMAc”), dimethylimidazolinone, tetramethylurea, dimethyl. Sulfoxide, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate, Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, propylene Glycol monomethyl ether acetate.

  Of these solvents, non-amide solvents are preferred because they have little influence on the photosensitizer. Specific examples of more preferable solvents include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate. From the viewpoint of (A) high solubility in an alkali-soluble resin and (B) prevention of precipitation of the photoacid generator with time, γ-butyrolactone is most preferred when used in combination with the above-mentioned solvent (C).

In the embodiment, the photosensitive resin composition for spin coating, (C) a 10Pa~250Pa vapor pressure at 25 ° C., and a density at 25 ° C. is at 0.7g ^/ cm ³ ~1.02g ^/ cm 3 The use of a mixed solvent having a mass ratio of a certain solvent and γ-butyllactone of 95: 5 to 30:70 is preferable because the film thickness uniformity of the prebaked film of the photosensitive resin composition for spin coating is improved. In addition, (C) a mixed solvent having a mass ratio of the solvent and γ-butyllactone of 90:10 to 40:60 achieves both a uniform film thickness of the pre-baked film and a reduction in the discharge mass during the production of the spin coat film. To more preferable.

Density for spin coating the photosensitive resin composition ^{is 0.75g / cm 3 ~1.1g / cm 3} . By setting the density within this range, it is possible to drastically reduce the discharge mass when forming the spin coat film. More preferably, the range of 0.95g / ^{cm 3} ~1.09g / ^cm 3 is preferred from the viewpoint of the uniformity of the discharge mass reduction and coating film.

  The viscosity at 25 ° C. of the photosensitive resin composition for spin coating is 0.5 Pa · s to 2 Pa · s. By setting the viscosity within this range, a film thickness required for a normal semiconductor protective film (3 μm to 20 μm for the final cured film) can be produced at an appropriate rotation speed (500 rpm to 5000 rpm) by a spin coating method. It becomes possible. Further, when the viscosity at 25 ° C. of the photosensitive resin composition for spin coating is in the range of 0.6 Pa · s to 1.5 Pa · s, the film thickness can be easily adjusted by the number of rotations during coating. More preferable. Regarding the unit of viscosity, it should be understood that 1 [P] is equal to 0.1 [Pa · s] (1P = 0.1 Pa · s).

(D) Crosslinking agent In the embodiment, in the case where the photosensitive resin composition for spin coating is used in a positive type, the negative coating is used for the purpose of increasing the chemical resistance of the heat-cured film (photosensitive resin layer). When used in a mold, (D) a cross-linking agent can be preferably used for the purpose of pattern formation as well as the purpose of increasing the chemical resistance of the film after thermosetting.

  (D) The crosslinking agent comprises an aromatic compound having a methylol group and / or an alkoxymethyl group, a compound substituted at the N-position with a methylol group and / or an alkoxymethyl group, an epoxy compound, an oxetane compound, and an allyl compound. At least one compound selected from the group can be used.

  Among these crosslinking agents, at least one compound selected from the group consisting of an aromatic compound having a methylol group and / or an alkoxymethyl group and a compound in which the N-position is substituted with a methylol group and / or an alkoxymethyl group is From the viewpoint of chemical resistance after thermosetting.

｛式中、Ｒ_１３は、水酸基であり、ｍ_３は、０〜３の整数であり、Ｒ_１４は、炭素数１〜３０の有機基であり、ｍ_４は、０〜３の整数であり、Ｒ_１５は、水素原子又は炭素数１〜８のアルキル基であり、ｍ_５は、１〜６の整数であり、そしてｍ３及びｍ５は、２≦（ｍ３＋ｍ５）≦６を満たす。｝ As an aromatic compound which has a methylol group and / or an alkoxymethyl group, what has a structure represented by following General formula (7) is preferable.

{In the formula, R ₁₃ is a hydroxyl group, m ₃ is an integer of 0 to 3, R ₁₄ is an organic group having 1 to 30 carbon atoms, and m ₄ is an integer of 0 to 3] , R ₁₅ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, m ₅ is an integer of 1 to 6, and m3 and m5 satisfy 2 ≦ (m3 + m5) ≦ 6. }

Specific examples of the aromatic compound having a methylol group and / or an alkoxymethyl group include the following compounds.

  More specifically, as a compound in which the N-position is substituted with a methylol group and / or an alkoxymethyl group, more specifically, melamine resin, benzoguanamine resin, glycoluril resin, hydroxyethylene urea resin, urea resin, glycol urea resin, alkoxymethylated melamine Mention may be made of resins, alkoxymethylated benzoguanamine resins, alkoxymethylated glycoluril resins, and alkoxymethylated urea resins.

  Among these, alkoxymethylated melamine resin, alkoxymethylated benzoguanamine resin, alkoxymethylated glycoluril resin, and alkoxymethylated urea resin are known methylolated melamine resin, methylolated benzoguanamine resin, or methylol of methylolated urea resin. It can be obtained by converting the group into an alkoxymethyl group. Examples of the kind of the alkoxymethyl group include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group.

  Specific examples of compounds in which the N-position is substituted with a methylol group and / or an alkoxymethyl group include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (manufactured by Mitsui Cytec Co., Ltd.), Nicarax MX-270, -280, -290, Nicarak MS-11, Nicarac MW-30, -100, -300,- 390, -750 (manufactured by Sanwa Chemical Co., Ltd.) and the like can be preferably used.

｛式中、Ｒ_１６及びＲ_１７は、それぞれ独立に、水素原子又は炭素数１〜８のアルキル基であり、そしてＲ_１８は、炭素数１〜３０の有機基である。｝ As the compound in which the N-position is substituted with a methylol group and / or an alkoxymethyl group, those having a structure represented by the following structure are preferable.

{Wherein R ₁₆ and R ₁₇ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ₁₈ is an organic group having 1 to 30 carbon atoms. }

Moreover, the monomer of the resin mentioned above can also be used as the (D) crosslinking agent, and examples thereof include the following compounds, hexamethoxymethylmelamine, dimethoxymethylurea and the like.

  The epoxy compound is a compound having a three-membered cyclic ether structure, and specific examples thereof include bisphenol A type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, glycidylamine type epoxy resin, polysulfide type epoxy. Examples include, but are not limited to, resins.

  An oxetane compound is a compound having a 4-membered cyclic ether structure, and is capable of a cationic ring-opening polymerization reaction or an addition reaction with carboxylic acid, thiol, or phenol. Specific examples of the oxetane compound include 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, bis [1-ethyl (3-oxetanyl)] methyl ether, 4,4′-bis. [(3-Ethyl-3-oxetanyl) methoxymethyl] biphenyl, 4,4′-bis (3-ethyl-3-oxetanylmethoxy) biphenyl, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, diethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, bis (3-ethyl-3-oxetanylmethyl) diphenoate, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3 -Oxetanylmethyl) ether, poly [ 3-[(3-ethyl-3-oxetanyl) methoxy] propyl] silasesquioxane] derivatives, oxetanyl silicate, phenol novolac oxetane, 1,3-bis [(3-ethyloxetane-3-yl) methoxy] benzene, Examples include, but are not limited to, OXT121 (Toagosei: trade name), OXT221 (Toagosei: trade name), and the like.

  Among these compounds, 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl, 4,4′-bis (3-ethyl-3-oxetanylmethoxy) from the viewpoint of heat resistance Biphenyl and OXT121 (Toagosei: trade name) are preferred.

  Specific examples of allyl compounds include allyl alcohol, allyl anisole, benzoic acid allyl ester, cinnamic acid allyl ester, N-allyloxyphthalimide, allyl phenol, allyl phenyl sulfone, allyl urea, diallyl phthalate, diallyl isophthalate, diallyl terephthalate , Diallyl maleate, diallyl isocyanurate, triallylamine, triallyl isocyanurate, triallyl cyanurate, triallylamine, triallyl 1,3,5-benzenetricarboxylate, triallyl trimelliate (TRIAM705 manufactured by Wako Pure Chemical Industries, Ltd.), pyromerit Examples include triallyl acid (TRIAM805 manufactured by Wako Pure Chemical Industries, Ltd.), triallyl oxydiphthalate, triallyl phosphate, triallyl phosphite, and triallyl citrate. However, it is not limited to these. From the viewpoint of sensitivity, triallyl trimellitic acid (TRIAM705 manufactured by Wako Pure Chemical Industries, Ltd.) and triallyl pyromellitic acid (TRIAM805 manufactured by Wako Pure Chemical Industries, Ltd.) are preferable.

  (D) A crosslinking agent can be used individually or in mixture of 2 or more types, A compounding quantity should be 1 mass part-100 mass parts with respect to 100 mass parts of (A) alkali-soluble resin. Preferably, it is 3 mass parts-50 mass parts. When the blending amount is 1 part by mass or more, crosslinking proceeds well and the patterning property becomes good. When the blending amount is 100 parts by mass or less, the mechanical properties after curing are kept good.

(E) Dissolution accelerator In the present invention, (E) a dissolution accelerator can be preferably used. (E) Examples of the dissolution accelerator include carboxylic acid compounds and phenolic compounds.

  Examples of carboxylic acid compounds include 3-phenyl lactic acid, 4-hydroxyphenyl lactic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4-hydroxy-3-methoxymandelic acid, 2-methoxy-2- ( 1-naphthyl) propionic acid, mandelic acid, atrolactic acid, acetylmandelic acid, α-methoxyphenylacetic acid, 3-phenyllactic acid, 4-hydroxyphenyllactic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4 -Hydroxy-3-methoxymandelic acid, 2-methoxy-2- (1-naphthyl) propionic acid, mandelic acid, atrolactic acid, O-acetylmandelic acid, α-methoxyphenylacetic acid, 4-hydroxymandelic acid, 3, 4-dihydroxymandelic acid, 4-hydroxy-3-methoxymandelic acid, Mandelic acid, atrolactic acid, O-acetylmandelic acid, α-methoxyphenylacetic acid, O-acetylmandelic acid, α-methoxyphenylacetic acid, hexyl dihydroxybenzenecarboxylate, octyl dihydroxybenzenecarboxylate, dodecyl dihydroxybenzenecarboxylate, tri Hexyl hydroxybenzenecarboxylate hexyl gallate and phloroglucinol carboxylate hexyl, octyl trihydroxybenzenecarboxylate octyl gallate and phloroglucinol carboxylate, dodecyl trihydroxybenzenecarboxylate dodecyl and fluorate Logucinol carboxylate dodecyl, trihydroxybenzenecarboxylate hexadecyl hexadecyl gallate and phloroglucinol carboxylate hex Sadecyl and the like can be mentioned.

  Examples of the phenolic compound include a ballast agent used in the photosensitive diazoquinone compound, and a linear phenol compound such as paracumylphenol, bisphenols, resorcinol, or MtrisPC, MtetraPC (made by Honshu Chemical Industry Co., Ltd .: trade name) ), Non-linear phenol compounds such as TrisP-HAP, TrisP-PHBA, TrisP-PA (made by Honshu Chemical Industry Co., Ltd .: trade name), compounds in which 2-5 hydrogen atoms of the phenyl group of diphenylmethane are substituted with hydroxyl groups, Examples include compounds in which 1 to 5 hydrogen atoms of the phenyl group of 2,2-diphenylpropane are substituted with hydroxyl groups. The addition of the phenolic compound can improve the adhesion of the relief pattern during development and suppress the generation of residues. In addition, a ballast agent means the phenol compound currently used as a raw material for the above-mentioned photosensitive diazoquinone compound which is a phenol compound in which a part of the phenolic hydrogen atom is converted to naphthoquinonediazide sulfonic acid ester.

  (E) The addition amount in the case of adding a dissolution accelerator is preferably 1 part by mass to 50 parts by mass, and more preferably 1 part by mass to 30 parts by mass with respect to 100 parts by mass of the total alkali-soluble resin. If the addition amount is 50 parts by mass or less, the heat resistance of the film after thermosetting is good.

(F) Other additives In the embodiment, the photosensitive resin composition for spin coating contains, as necessary, a surfactant, a silicon substrate for improving in-plane uniformity of the dye, fragrance, and coating film. Or additives, such as an adhesion aid for improving adhesiveness with a copper substrate, can also be contained.

  Examples of the dye include methyl violet, crystal violet, and malachite green. As for the compounding quantity of dye, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of (A) alkali-soluble resin. If the blending amount is 0.1 parts by mass or more, the visualization effect is obtained well, and if it is 10 parts by mass or less, the heat resistance of the film after thermosetting is good.

Examples of the perfume include terpene compounds, and monoterpene compounds and sesquiterpene compounds are preferable from the viewpoint of solubility in solvents.
Specifically, as the fragrance, for example, linalool, isophytol, dihydrolinalol, linalool acetate, linalool oxide, geranyl linalool, lavandulol, tetrahydrolabandulol, lavandulol acetate, nerol, nerol acetate, geraniol, citral , Geranyl acetate, geranylacetone, geraniic acid, citral dimethyl acetal, citronellol, citronellal, hydroxycitronellal, dimethyl octanal, citronellyl acid, citronellyl acetate, tageton, artemisia ketone, pregol, isopulegol, menthol, menthol acetate, iso Menthol, neomenthol, mentanol, menthanetriol, menthanetetraol, carbomenthol, menthoxyacetic acid, perillyl alcohol , Perilaldehyde, carbeol, piperitol, terpene-4-ol, terpineol, terpineol, dihydroterpineol, sobreol, thymol, borneol, bornyl acetate, isoborneol, isobornyl acetate, cineol, pinol, pinocarbeveol, myrtenol, myrtenal, Examples include berbenol, pinocamphetol, camphorsulfonic acid, nerolidol, terpinene, ionone, pinene, camphene, camphorene aldehyde, camphoronic acid, isocamphoronic acid, camphoric acid, abitienic acid, glycyrrhetinic acid and the like. These terpene compounds may be used alone or in combination of two or more.

  0.1 mass part-70 mass parts are preferable with respect to 100 mass parts of (A) alkali-soluble resin, and, as for the compounding quantity of a fragrance | flavor, 1 mass part-50 mass parts are more preferable. If the blending amount is 0.1 parts by mass, the effect of the fragrance is obtained satisfactorily, and if it is 70 parts by mass or less, the heat resistance of the film after thermosetting is good.

  Examples of the surfactant include polyglycols such as polypropylene glycol and polyoxyethylene lauryl ether, and nonionic surfactants composed of derivatives thereof. Further, fluorine-based surfactants such as Fluorard (manufactured by Sumitomo 3M: trade name), Megafuck (manufactured by Dainippon Ink & Chemicals, Inc .: trade name), Lumiflon (trade name, manufactured by Asahi Glass Co., Ltd.), and the like can be mentioned. Furthermore, organosiloxane surfactants such as KP341 (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name), DBE (manufactured by Chisso Corporation: trade name), granol (manufactured by Kyoeisha Chemical Co., Ltd .: trade name), and the like can be mentioned. By adding the surfactant, it is possible to make it less likely to cause repellency of the coating film at the wafer edge during coating.

  0-10 mass parts is preferable with respect to 100 mass parts of (A) alkali-soluble resin, and, as for the compounding quantity of surfactant, 0.01 mass part-1 mass part are more preferable. When the blending amount is 10 parts by mass or less, the heat resistance of the film after thermosetting is good. Moreover, when a compounding quantity is 0.01 mass part or more, the effect which prevents the repelling of said coating film is favorable.

  Examples of the adhesion assistant for improving the adhesion between the cured resist pattern and the silicon substrate or the copper substrate include alkyl imidazoline, polyhydroxystyrene, polyvinyl methyl ether, t-butyl novolac, epoxy polymer, organosilicon compound, and triazole. , Tetrazole, oxazole, thiazole, imidazole and the like.

  An organosilicon compound is a compound containing a mono- or higher functional alkoxyl group and a silanol group, and serves as an adhesion aid for enhancing adhesion to a silicon wafer. From the viewpoint of solubility in a solvent, the number of carbon atoms of the organosilicon compound is preferably 4-30, and more preferably 4-18.

  Specific examples of the organosilicon compound include 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name KBM803, manufactured by Chisso Corporation: trade name of Silaace S810), 3-mercaptopropyltriethoxysilane (AZMAX Corporation). Manufactured by trade name: SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name: LS1375, manufactured by Azumax Co., Ltd .: tradename: SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azumax Corporation) : Trade name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by Azmax Co., Ltd .: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydi Toxisilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercaptoethyltri Methoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxy Propoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-methyl Captobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, N- (3-triethoxysilylpropyl) urea (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name LS3610, manufactured by Asmax Co., Ltd .: trade name SIU9055.0), N -(3-trimethoxysilylpropyl) urea (manufactured by Azmax Co., Ltd .: trade name SIU9058.0), N- (3-diethoxymethoxysilylpropyl) urea, N- (3-ethoxydimethoxysilylpropyl) urea, N- (3-Tripropoxysilylpropyl) urea, N- (3-diethoxypropoxysilylpropyl) urea, N- (3-ethoxydipropoxysilylpropyl) urea, N- (3-dimethoxypropoxysilylpropyl) urea, N- (3-methoxydipropoxysilyl group (Lopyl) urea, N- (3-trimethoxysilylethyl) urea, N- (3-ethoxydimethoxysilylethyl) urea, N- (3-tripropoxysilylethyl) urea, N- (3-tripropoxysilylethyl) Urea, N- (3-ethoxydipropoxysilylethyl) urea, N- (3-dimethoxypropoxysilylethyl) urea, N- (3-methoxydipropoxysilylethyl) urea, N- (3-trimethoxysilylbutyl) Urea, N- (3-triethoxysilylbutyl) urea, N- (3-tripropoxysilylbutyl) urea, 3- (m-aminophenoxy) propyltrimethoxysilane (manufactured by Azmax Co., Ltd .: trade name SLA0598.0) , M-aminophenyltrimethoxysilane (manufactured by AZMAX Co., Ltd .: commodity SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.1) aminophenyltrimethoxysilane (manufactured by Azmax Corporation: trade name SLA0599.2), 2- (trimethoxysilylethyl) Pyridine (manufactured by Azmax Co., Ltd .: trade name SIT8396.0), 2- (triethoxysilylethyl) pyridine, 2- (dimethoxysilylmethylethyl) pyridine, 2- (diethoxysilylmethylethyl) pyridine, (3-triethoxy (Silylpropyl) -t-butylcarbamate, (3-glycidoxypropyl) triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, Tra-i-butoxysilane, tetra-t-butoxysilane, tetrakis (methoxyethoxysilane), tetrakis (methoxy-n-propoxysilane), tetrakis (ethoxyethoxysilane), tetrakis (methoxyethoxyethoxysilane), bis (trimethoxy Silyl) ethane, bis (trimethoxysilyl) hexane, bis (triethoxysilyl) methane, bis (triethoxysilyl) ethane, bis (triethoxysilyl) ethylene, bis (triethoxysilyl) octane, bis (triethoxysilyl) Octadiene, bis [3- (triethoxysilyl) propyl] disulfide, bis [3- (triethoxysilyl) propyl] tetrasulfide, di-t-butoxydiacetoxysilane, di-i-butoxyaluminoxytriethoxysilane Orchid, bis (pentadionate) titanium-O, O'-bis (oxyethyl) -aminopropyltriethoxysilane, phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilane Diol, n-butyldiphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n-propylmethylphenyl Silanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol tert-butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenyl Examples thereof include, but are not limited to, silanol, isopropyl diphenyl silanol, n-butyl diphenyl silanol, isobutyl diphenyl silanol, tert-butyl diphenyl silanol, and triphenyl silanol. These may be used alone or in combination.

As the organosilicon compound, among the aforementioned organosilicon compounds, from the viewpoint of storage stability, phenylsilanetriol, trimethoxyphenylsilane, trimethoxy (p-tolyl) silane, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane , Dimethoxydi-p-tolylsilane, triphenylsilanol, and a silane coupling agent represented by the following structure are preferable.

  The organosilicon compounds may be used alone or in combination of two or more. When the organosilicon compound is blended, the blending amount is preferably 1 to 40 parts by weight, more preferably 2 to 30 parts by weight, with respect to 100 parts by weight of the (A) alkali-soluble resin. 20 parts by mass is more preferable. If the compounding amount of the compound is 1 part by mass or more, the development residue in the exposed part is reduced satisfactorily and the adhesion to the silicon substrate is good. On the other hand, if it is 40 parts by mass or less, the cured film Tensile elongation is good, and shows good adhesion and lithography performance.

｛式中、Ｚ_１は、水素原子、炭素原子数１〜５の１価の炭化水素基、及びカルボキシル基から成る群から選ばれる基であり、Ｚ_２は、水素原子、ヒドロキシル基、炭素原子数１〜５の１価の炭化水素基、及びアミノアルキル基から成る群から選ばれる少なくとも１つの基である。｝ Specific examples of the heterocyclic structure compound include 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 1,3-dimethyl-5-pyrazolone, 3,5-dimethylpyrazole, 5,5-dimethylhydantoin, 3-methyl- 5-pyrazolone, 3-methyl-1-phenyl-5-pyrazolone, 2-methylimidazole, 1,10-phenanthroline, phenothiazine, phenoxazine, phenoxatin, mercaptobenzothiazole, mercaptobenzoxazole, methylthiobenzothiazole, dibenzothiazyl disulfide , Methylthiobenzimidazole, benzimidazole, phenylmercaptothiazoline, mercaptophenyltetrazole, and mercaptomethyltetrazole. Examples of benzotriazoles include compounds represented by the following general formula.

{In the formula, Z ₁ is a group selected from the group consisting of a hydrogen atom, a monovalent hydrocarbon group having 1 to 5 carbon atoms, and a carboxyl group; Z ₂ is a hydrogen atom, a hydroxyl group, a carbon atom; It is at least one group selected from the group consisting of a monovalent hydrocarbon group of 1 to 5 and an aminoalkyl group. }

Among heterocyclic structure compounds, from the viewpoint of sensitivity on a copper substrate, from 5-mercapto-1-phenyltetrazole, 1,2,3-benzotriazole, benzothiazole, benzoxazole, benzimidazole, and 2-mercaptobenzoxazole More preferred are compounds selected from the group consisting of:
These heterocyclic structure compounds may be used alone or in combination of two or more.

  0.1-30 mass parts is preferable with respect to 100 mass parts of (A) alkali-soluble resin, and, as for the compounding quantity of a heterocyclic structure compound, 0.5 mass part-10 mass parts are more preferable. When the compounding amount of the heterocyclic structure compound is 0.1 parts by mass or more, the adhesiveness of the heat-cured film to the copper substrate is good, and when it is 30 parts by mass or less, the stability of the composition is good.

<Curing relief pattern and method for manufacturing semiconductor device>
Further, the present invention is a method for producing a cured relief pattern,
(A) a step of forming a photosensitive resin layer or a photosensitive film comprising the photosensitive resin composition for spin coating of the present invention on a substrate by a spin coating method;
(B) a step of exposing the photosensitive resin layer or the photosensitive film;
(C) removing the exposed or unexposed portion of the photosensitive resin layer or photosensitive film with a developer to obtain a relief pattern; and (d) heating the relief pattern.
A method comprising:

Moreover, this invention provides the hardening relief pattern manufactured by the said method. Steps (a) to (d) will be specifically described below.
(A) a step of forming a photosensitive resin layer or photosensitive film comprising the photosensitive resin composition for spin coating of the present invention on a substrate by a spin coating method;
The photosensitive resin composition for spin coating of the present invention is applied to a substrate such as a silicon wafer, a ceramic substrate, or an aluminum substrate using a spin coater, and then 50 ° C. to 140 ° C. using an oven or a hot plate. Dry with to remove the solvent.
(B) a step of exposing the photosensitive resin layer or the photosensitive film;
Next, the substrate obtained above is exposed to actinic radiation through a mask using a contact aligner or a stepper, or directly irradiated with a light beam, an electron beam or an ion beam.
(C) removing the exposed or unexposed portions of the photosensitive resin layer or photosensitive film with a developer to obtain a relief pattern;
Next, development can be performed by selecting from methods such as dipping, paddle, and rotary spraying. By development, an exposed portion (in the case of a positive type) or an unexposed portion (in the case of a negative type) can be eluted and removed from the applied photosensitive resin composition to obtain a relief pattern. Developers include inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide. An aqueous solution such as a quaternary ammonium salt such as quaternary ammonium salt and an aqueous solution to which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added as required can be used. Among these, tetramethylammonium hydroxide aqueous solution is preferable, and the concentration of the tetramethylammonium hydroxide is preferably 0.5% by mass to 10% by mass, and more preferably 1% by mass to 5% by mass. It is.
(D) heating the relief pattern;
Finally, the obtained relief pattern is cured to form a heat-resistant cured relief pattern made of a resin having a polybenzoxazole structure. As the heating device, an oven furnace, a hot plate, a vertical furnace, a belt conveyor furnace, a pressure oven, or the like can be used. As a heating method, heating by hot air, infrared rays, electromagnetic induction, or the like is recommended. The temperature is preferably 200 ° C to 450 ° C, more preferably 250 ° C to 400 ° C. The heating time is preferably 15 minutes to 8 hours, more preferably 15 minutes to 4 hours. The atmosphere during heating is preferably in an inert gas such as nitrogen or argon.

  The present invention also provides a semiconductor device comprising a semiconductor element and a cured film provided on the semiconductor element, wherein the cured film is the cured relief pattern of the present invention. Examples of the cured film include a passivation film on a semiconductor element, a protective film such as a buffer coat film formed by forming a cured film of the above-described photosensitive resin composition on the passivation film, and a circuit formed on the semiconductor element. Examples thereof include an insulating film such as an interlayer insulating film formed by forming a cured film of the above-described photosensitive resin composition, an α-ray blocking film, a planarizing film, a protrusion (resin post), a partition wall, and the like.

  The present invention also provides a display device comprising a display element and a cured film provided on the display element, wherein the cured film is the cured relief pattern of the present invention. To do. Applications of the display device include, for example, a protective film formed by forming a cured film of the above-described photosensitive resin composition on the display element, an insulating film or a flattening film for TFT elements or color filters, MVA type, etc. Examples thereof include protrusions for liquid crystal display devices, partition walls for organic EL element cathodes, and the like. The use method is based on forming the cured film of the photosensitive resin composition patterned on the substrate on which the display element or the color filter is formed according to the use of the semiconductor device by the above method.

  The photosensitive resin composition of the present invention is also useful for applications such as interlayer insulation for multilayer circuits, cover coats for flexible copper-clad plates, solder resist films, liquid crystal alignment films for display devices, and light emitting elements. .

Synthesis Example 1 Synthesis of Hydroxy Polyamide (P-1) In a 2 L separable flask, 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane (hereinafter also referred to as “6FAP”) ) 197.8 g (0.54 mol), 75.9 g (0.96 mol) of pyridine, and 692 g of DMAc were mixed and stirred at room temperature (25 ° C.) to dissolve. To the obtained mixture, a mixed solution in which 19.7 g (0.12 mol) of 5-norbornene-2,3-dicarboxylic anhydride was separately dissolved in 88 g of GBL was dropped from a dropping funnel. The time required for the dropwise addition was 40 minutes, and the maximum reaction solution temperature was 28 ° C.
After completion of the dropwise addition, the flask was heated to 50 ° C. with a hot water bath and stirred for 18 hours, and then the IR spectrum of the reaction solution was measured. Characteristic absorptions of imide groups at 1385 cm ⁻¹ and 1772 cm ⁻¹ appeared. It was confirmed.
Next, the flask was cooled to 8 ° C. with a water bath, and a mixed solution in which 142.3 g (0.48 mol) of 4,4′-diphenyl ether dicarboxylic acid dichloride was separately dissolved in 398 g of GBL was dropped from a dropping funnel. The time required for the dropping was 80 minutes, and the maximum reaction solution temperature was 12 ° C. Three hours after the completion of dropping, the reaction solution was dropped into 12 l of water under high-speed stirring to disperse and precipitate the polymer. The purified precipitate was recovered, washed with water as appropriate, dehydrated and then vacuum dried to obtain polyhydroxyamide (P-1). The weight average molecular weight of the thus synthesized hydroxypolyamide according to gel permeation chromatography (GPC) was 14,000 in terms of polystyrene. The analysis conditions for GPC are described below.
Column: Trade name Shodex 805/804/803 series Mobile phase: Tetrahydrofuran 40 ° C
Flow rate: 1.0 ml / min Detector: Showa Denko brand name Shodex RI SE-61

を有するＴＭＯＭ−ＢＰ（本州化学社製：商品名）２１．７ｇ（０．０６ｍｏｌ）、ピリジン９．４８ｇ（０．１２ｍｏｌ）及びＧＢＬ１３０ｇを０℃で混合攪拌した溶液に、別途ＧＢＬ１４２ｇ中にビス（クロロカルボニル）トリシクロ［５，２，１，０^２，６］デカンを４７．５ｇ（０．１８ｍｏｌ）を溶解させたものを、滴下ロートより滴下した。滴下に要した時間は４０分、反応液温は最大で１６℃であった。
滴下後、１時間攪拌した反応溶液を、滴下ロートを用いて、別途、テフロン（登録商標）製の碇型攪拌器を取り付けた容量２Ｌのセパラブルフラスコ中で、６ＦＡＰ５１．２ｇ（０．１４ｍｏｌ）、ピリジン１５．０ｇ（０．１９ｍｏｌ）、ＧＢＬ３０７ｇ及びＤＭＡｃ１０２ｇを室温（２５℃）で混合攪拌し溶解させ、その反応容器をメタノールにドライアイスを加えた容器に浸して−１５℃に冷却した反応溶液に、滴下した。反応系中は−１５〜０℃に保って４５分を要して反応容器に滴下した。滴下終了後、反応容器を氷浴に浸し、０〜１０℃に保って１時間攪拌した。さらにピリジン７．１２ｇ（０．０９ｍｏｌ）を加えた。その後、反応液を室温に戻し、５−ノルボルネン−２，３−ジカルボン酸無水物（東京化成工業社製）１９．７ｇ（０．１２ｍｏｌ）とピリジン９．４９ｇ（０．１２ｍｏｌ）を加え、５０℃の湯浴に浸して、反応液を５０℃とし１８時間攪拌した。
上記反応液にエタノールを加えて重合体を析出させた後、回収し、ＧＢＬ６２６ｇに溶解させた。次いで、陽イオン交換樹脂（オルガノ社製、アンバーリストＡ２１）６２．１ｇ、陰イオン交換樹脂（オルガノ社製、アンバーリスト１５）５９．６ｇでイオン交換した。この溶液をイオン交換水１２Ｌに高速攪拌下で滴下し、重合体を分散析出させ、回収し、適宜水洗、脱水の後に真空乾燥を施し、ＰＢＯ前駆体構造と架橋基含有構造を有するアルカリ可溶性重合体（Ｐ−２）の紛体を得た。
このようにして合成されたアルカリ可溶性重合体のＧＰＣによる重量平均分子量（Ｍｗ）は、ポリスチレン換算で１３２００の単一のシャープな曲線であり、単一組成物であった。 [Synthesis Example 2] Synthesis of Hydroxy Polyamide (P-2) In a 300 mL three-necked flask equipped with a Teflon (registered trademark) vertical stirrer, the following structure:

TMOM-BP (made by Honshu Chemical Co., Ltd .: trade name) 21.7 g (0.06 mol), pyridine 9.48 g (0.12 mol) and GBL 130 g were mixed and stirred at 0 ° C. with bis ( the chlorocarbonyl) tricyclo [5,2,1,0 ^2,6] decane obtained by dissolving a 47.5 g (0.18 mol), was added dropwise from the dropping funnel. The time required for the dropwise addition was 40 minutes, and the maximum reaction solution temperature was 16 ° C.
After the dropwise addition, the reaction solution stirred for 1 hour was separately added using a dropping funnel in a separable flask having a capacity of 2 L equipped with a vertical stirrer made of Teflon (registered trademark) and 51.2 g (0.14 mol) of 6FAP. , 15.0 g (0.19 mol) of pyridine, 307 g of GBL and 102 g of DMAc were mixed and stirred at room temperature (25 ° C.), dissolved, and the reaction vessel was immersed in a vessel obtained by adding dry ice to methanol and cooled to −15 ° C. It was dripped. The reaction system was maintained at -15 to 0 ° C. and took 45 minutes, and was dropped into the reaction vessel. After completion of the dropwise addition, the reaction vessel was immersed in an ice bath and kept at 0 to 10 ° C. and stirred for 1 hour. Further, 7.12 g (0.09 mol) of pyridine was added. Thereafter, the reaction solution was returned to room temperature, 19.7 g (0.12 mol) of 5-norbornene-2,3-dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 9.49 g (0.12 mol) of pyridine were added, and 50 The reaction solution was immersed in a hot water bath at 50 ° C. and stirred for 18 hours.
Ethanol was added to the reaction solution to precipitate a polymer, and then recovered and dissolved in 626 g of GBL. Subsequently, ion exchange was performed with 62.1 g of a cation exchange resin (manufactured by Organo, Amberlyst A21) and 59.6 g of an anion exchange resin (manufactured by Organo, Amberlyst 15). This solution is dropped into 12 L of ion-exchanged water under high-speed stirring, and the polymer is dispersed and precipitated, recovered, appropriately washed with water, dehydrated and then vacuum-dried to obtain an alkali-soluble heavy having a PBO precursor structure and a crosslinking group-containing structure. A powder of coalesced (P-2) was obtained.
The weight average molecular weight (Mw) by GPC of the alkali-soluble polymer synthesized in this way was a single sharp curve of 13200 in terms of polystyrene, and was a single composition.

Synthesis Example 3 Synthesis of Hydroxy Polyamide (P-3) In a 2 L separable flask equipped with a Teflon (registered trademark) vertical stirrer, 6FAP 51.2 g (0.14 mol), pyridine 15.0 g (0.19 mol), 307 g of GBL and 102 g of DMAc were added, mixed and stirred at room temperature (25 ° C.) to dissolve, and the reaction vessel was immersed in a vessel obtained by adding dry ice to methanol and cooled to −15 ° C. Separately, a mixed solution prepared by dissolving 26.56 g (0.09 mol) of 4,4′-diphenyl ether dicarboxylic acid dichloride in 132 g of GBL was dropped from the dropping funnel. In the reaction system, it was kept at -15 to 0 ° C. and took 45 minutes to drop into the reaction vessel (reaction liquid 1).
Separately, TMOM-BP (Honshu Chemical: trade name) 10.9 g (0.03 mol), 4,4-biphenol 0 was placed in a 300 mL three-necked flask equipped with a Teflon (registered trademark) vertical stirrer. .93 g (0.005 mol) 9.48 g (0.12 mol) of pyridine and 130 g of GBL were mixed and stirred at 0 ° C., and bis (chlorocarbonyl) tricyclo [5,2,1,0 0 ^2,6 ] separately in 142 g of GBL. A solution in which 23.75 g (0.09 mol) of decane was dissolved was dropped from a dropping funnel. The time required for the dropwise addition was 40 minutes, and the maximum reaction solution temperature was 16 ° C. After dropping, the mixture was stirred for 1 hour (reaction solution 2).
(Reaction solution 2) was added dropwise to (reaction solution 1) using a dropping funnel. The time required for the dropping was 40 minutes, and the maximum reaction temperature was 6 ° C. After the completion, the reaction vessel was immersed in an ice bath and kept at 0 to 10 ° C. and stirred for 1 hour. Further, 7.12 g (0.09 mol) of pyridine was added. Thereafter, the reaction solution was returned to room temperature, 19.7 g (0.12 mol) of 5-norbornene-2,3-dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 9.49 g (0.12 mol) of pyridine were added, and 50 The reaction solution was immersed in a hot water bath at 50 ° C. and stirred for 18 hours.
Ethanol was added to the reaction solution to precipitate a polymer, and then recovered and dissolved in 626 g of GBL. Subsequently, ion exchange was performed with 62.1 g of a cation exchange resin (manufactured by Organo, Amberlyst A21) and 59.6 g of an anion exchange resin (manufactured by Organo, Amberlyst 15). This solution is dropped into 12 L of ion-exchanged water under high-speed stirring, and the polymer is dispersed and precipitated, recovered, appropriately washed with water, dehydrated and then vacuum-dried to obtain an alkali-soluble heavy having a PBO precursor structure and a crosslinking group-containing structure. A powder (P-3) was obtained.
The weight-average molecular weight (Mw) by GPC of the alkali-soluble polymer thus synthesized was a single sharp curve of 11300 in terms of polystyrene, and was a single composition.

[Synthesis Example 4] Synthesis of polyamide (P-4) derived from tetracarboxylic acid and diamine and having a carboxyl group at the ortho position of the amide bond. A stirrer, thermometer, nitrogen inlet tube, and Dimroth condenser tube were provided. In a 5 liter flask, 295.0 g of N-methyl-2-pyrrolidone, 55.3 g of 2-octanone and 36.9 g of diethyl ketone were charged, 26.21 g of 4,4′-diaminodiphenyl ether, bis (3-aminophenoxy). 14.70 g of phenyl) sulfone and LP7100 (trade name, 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane) manufactured by Shin-Etsu Chemical Co., Ltd. were added and stirred. Dissolved. Next, 50.02 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added to this solution, followed by stirring at 25 ° C. for 8 hours and then at 60 ° C. for 8 hours for reaction. The polyamic acid solution thus obtained was dropped into 5 L of ion-exchanged water under high-speed stirring, the polymer was dispersed and precipitated, recovered, appropriately washed with water, dehydrated and then vacuum dried to obtain an alkali having a polyamic acid structure. A soluble polymer (P-4) powder was obtained. The weight-average molecular weight (Mw) by GPC of the alkali-soluble polymer thus synthesized was a single sharp curve of 26400 in terms of polystyrene, and was a single composition.

Synthesis Example 5 Synthesis of alkaline aqueous solution-soluble polyimide (P-5) having a phenolic hydroxyl group in the side chain 6FAP 32. In a four-necked flask equipped with a stirrer, a Dean-Stark trap with a ball, and a nitrogen introduction tube. 96 g (90 mmol was added, 196 g of NMP and 40 g of toluene were added, and the mixture was stirred at room temperature. Next, 31.02 g (100 mmol) of 3,3,4,4-oxydiphthalic dianhydride was added, and the mixture was stirred at room temperature for 2 hours. Next, the mixture was heated and stirred at 180 ° C. and 180 rpm for 3 hours, and during the reaction, water as a by-product was distilled azeotropically with toluene, and water accumulated at the bottom of the reflux tube was removed every 30 minutes. The weight average molecular weight in terms of polystyrene of the polyimide polymer thus produced was 24400. This reaction solution was dropped into 5 L of water under high-speed stirring, Rimmer allowed to disperse precipitate, which was collected, appropriately washed with water to obtain a powder of the alkali-soluble polymer having a soluble polyimide structure in an organic solvent subjected to vacuum drying after dehydration (P-5).

｛式中、Ｑは、全体数の８３％が下記式：

で表される構造であり、残りの１７％が水素原子である。｝
(Ｃ)２５℃における蒸気圧が１０Ｐａ〜２５０Ｐａであり、かつ２５℃における密度が０．７ｇ／ｃｍ^３〜１．０２ｇ／ｃｍ^３である溶媒として下記（Ｃ−１）〜（Ｃ−９）を用い、その他の溶媒として下記（Ｘ−１）〜（Ｘ−８）を用いた。 <Preparation of photosensitive resin composition>
(A) As an alkali-soluble resin, (P-1) to (P-5) obtained in Synthesis Examples 1 to 5 above, a phenol resin (trade name: EP4000B, m-cresol / p-cresol ratio = 60/40) Asahi Organic Materials Co., Ltd.) (P-6) and polyhydroxystyrene (manufactured by Maruzen Petrochemical Co., Ltd .: trade name Marcalinker CST) (P-7). Using a compound represented by the structure (hereinafter also referred to as PAC1),

{In the formula, Q is 83% of the total number:

The remaining 17% are hydrogen atoms. }
(C) a 10Pa~250Pa vapor pressure at 25 ° C., and the following as the solvent is the density at 25 ° C. is ^{0.7g / cm 3 ~1.02g / cm 3} (C-1) ~ (C-9) The following (X-1) to (X-8) were used as other solvents.

The solvents used and their vapor pressure and density at 25 ° C. are shown below:
(C-1) 2-octanone (vapor pressure 233 Pa, density 0.81 g / cm ³ )
(C-2) 2-nonanone (vapor pressure 85 Pa, density 0.82 g / cm ³ )
(C-3) Diisobutyl ketone (vapor pressure 197 Pa, density 0.81 g / cm ³ )
(C-4) Isoamyl ether (vapor pressure 225 Pa, density 0.79 g / cm ³ )
(C-5) 1-heptanol (vapor pressure 43 Pa, density 0.82 g / cm ³ )
(C-6) 2-ethyl-1-hexanol (vapor pressure 27 Pa, density 0.82 g / cm ³ )
(C-7) Propylene glycol monobutyl ether (vapor pressure 59 Pa, density 0.89 g / cm ³ )
(C-8) Dipropylene glycol dimethyl ether (vapor pressure 70 Pa, density 0.91 g / cm ³ )
(C-9) Dipropylene glycol methyl propyl ether (vapor pressure 30 Pa, density 0.90 g / cm ³ )
(X-1) GBL (vapor pressure 36 Pa, density 1.13 g / cm ³ )
(X-2) N-methylpyrrolidone (vapor pressure 40 Pa, density 1.03 g / cm ³ )
(X-3) Ethyl lactate (vapor pressure 155 Pa, density 1.05 g / cm ³ )
(X-4) PGMEA (vapor pressure 420 Pa, density 0.96 g / cm ³ )
(X-5) 2-Heptanone (vapor pressure 630 Pa, density 0.81 g / cm ³ )
(X-6) Dibutyl ether (vapor pressure 946 Pa, density 0.78 g / cm ³ )
(X-7) Dipropylene glycol monobutyl ether (vapor pressure 8 Pa, density 0.93 g / cm ³ )
(X-8) Propylene carbonate (vapor pressure 4 Pa, density 1.17 g / cm ³ )

[Example 1]
(A) P-1 synthesized in Synthesis Example 1 is used as the alkali-soluble resin, 15 parts by mass of (B) photoacid generator PAC1 is blended with 100 parts by mass of P-1, and C- 1 was used to adjust the composition so that the viscosity was 10P. A positive photosensitive resin composition was prepared by filtration through a polyethylene filter having pores of 0.2 μm.

[Example 2]
A positive photosensitive resin composition was similarly prepared using P-2 synthesized in Synthesis Example 2 instead of P-1 used in Example 1.

[Example 3]
A positive photosensitive resin composition was similarly prepared using P-3 synthesized in Synthesis Example 3 instead of P-1 used in Example 1.

[Example 4]
A positive photosensitive resin composition was similarly prepared using P-4 synthesized in Synthesis Example 4 instead of P-1 used in Example 1.

[Example 5]
A positive photosensitive resin composition was similarly prepared using P-5 synthesized in Synthesis Example 5 instead of P-1 used in Example 1.

[Example 6]
A positive photosensitive resin composition was similarly prepared using phenol resin P-6 instead of P-1 used in Example 1.

[Example 7]
A positive photosensitive resin composition was similarly prepared using polyhydroxystyrene P-7 instead of P-1 used in Example 1.

[Example 8]
A positive photosensitive resin composition was similarly prepared using the solvent C-8 instead of the solvent C-1 used in Example 1.

[Example 9]
A positive photosensitive resin composition was similarly prepared using P-2 synthesized in Synthesis Example 2 instead of P-1 used in Example 8.

[Example 10]
A positive photosensitive resin composition was similarly prepared using P-3 synthesized in Synthesis Example 3 instead of P-1 used in Example 8.

[Example 11]
A positive photosensitive resin composition was similarly prepared using P-4 synthesized in Synthesis Example 4 instead of P-1 used in Example 8.

[Example 12]
A positive photosensitive resin composition was similarly prepared using P-5 synthesized in Synthesis Example 5 instead of P-1 used in Example 8.

[Example 13]
A positive photosensitive resin composition was similarly prepared using phenol resin P-6 instead of P-1 used in Example 8.

[Example 14]
A positive photosensitive resin composition was similarly prepared using polyhydroxystyrene P-7 instead of P-1 used in Example 8.

[Example 15]
A positive photosensitive resin composition was similarly prepared using the solvent C-2 instead of the solvent C-1 used in Example 1.

[Example 16]
A positive photosensitive resin composition was similarly prepared using the solvent C-3 instead of the solvent C-1 used in Example 1.

[Example 17]
A positive photosensitive resin composition was similarly prepared using the solvent C-4 instead of the solvent C-1 used in Example 1.

[Example 18]
A positive photosensitive resin composition was prepared in the same manner using the solvent C-5 instead of the solvent C-1 used in Example 1.

[Example 19]
A positive photosensitive resin composition was prepared in the same manner using the solvent C-6 instead of the solvent C-1 used in Example 1.

[Example 20]
A positive photosensitive resin composition was similarly prepared using the solvent C-7 instead of the solvent C-1 used in Example 1.

[Example 21]
A positive photosensitive resin composition was similarly prepared using the solvent C-9 instead of the solvent C-1 used in Example 1.

[Example 22]
(A) As alkali-soluble resin, P-1 synthesized in Synthesis Example 1 and phenol resin P-6 were prepared by mixing at a mass ratio of 100: 50. B) 15 parts by mass of the photoacid generator PAC1 was blended, and the composition was adjusted using C-8 as a solvent so that the viscosity was 10P. A positive photosensitive resin composition was prepared by filtration through a polyethylene filter having pores of 0.2 μm.

[Example 23]
Positive photosensitivity in the same manner as in Example 22 except that (A) the alkali-soluble resin prepared by mixing P-1 synthesized in Synthesis Example 1 and phenol resin P-6 at a mass ratio of 100: 100 was used. A resin composition was prepared.

[Example 24]
Positive photosensitivity in the same manner as in Example 22 except that (A) the alkali-soluble resin prepared by mixing P-1 synthesized in Synthesis Example 1 and phenol resin P-6 at a mass ratio of 100: 150 was used. A resin composition was prepared.

[Example 25]
Positive photosensitivity in the same manner as in Example 22 except that (A) the alkali-soluble resin prepared by mixing P-3 synthesized in Synthesis Example 3 and phenol resin P-6 at a mass ratio of 100: 50 was used. A resin composition was prepared.

[Example 26]
Positive photosensitivity in the same manner as in Example 22 except that P-3 synthesized in Synthesis Example 3 and phenol resin P-6 were mixed at a mass ratio of 100: 100 and replaced with (A) alkali-soluble resin. A resin composition was prepared.

[Example 27]
Positive photosensitivity in the same manner as in Example 22 except that (A) the alkali-soluble resin prepared by mixing P-3 synthesized in Synthesis Example 3 and phenol resin P-6 at a mass ratio of 100: 150 was used. A resin composition was prepared.

[Example 28]
(A) As an alkali-soluble resin, using P-1 synthesized in Synthesis Example 1, 15 parts by mass of (B) photoacid generator PAC1 is blended with respect to 100 parts by mass of P-1, and used as a solvent. A composition was prepared using a mixture of C-1 and X-1 at a mass ratio of 20:80 so that the viscosity was 10P. A positive photosensitive resin composition was prepared by filtration through a polyethylene filter having pores of 0.2 μm.

[Example 29]
A positive photosensitive resin composition was prepared in the same manner as in Example 28 except that a solvent in which C-1 and X-1 were mixed at a mass ratio of 50:50 was used.

[Example 30]
A positive photosensitive resin composition was prepared in the same manner as in Example 28 except that a solvent in which C-1 and X-1 were mixed at a mass ratio of 80:20 was used.

[Example 31]
A positive photosensitive resin composition was prepared in the same manner as in Example 28 except that a solvent in which C-8 and X-1 were mixed at a mass ratio of 40:60 was used.

[Example 32]
A positive photosensitive resin composition was prepared in the same manner as in Example 28 except that C-8 and X-1 mixed at a mass ratio of 50:50 were used as the solvent.

[Example 33]
A positive photosensitive resin composition was prepared in the same manner as in Example 28 except that C-8 and X-1 were mixed at a mass ratio of 80:20 as a solvent.

[Example 34]
A positive photosensitive resin composition was prepared in the same manner as in Example 1 except that the viscosity of the varnish was adjusted to 5P.

[Example 35]
A positive photosensitive resin composition was prepared in the same manner as in Example 1 except that the viscosity of the varnish was adjusted to 20P.

[Comparative Example 1]
A positive photosensitive resin composition was similarly prepared using the solvent X-1 instead of the solvent C-1 used in Example 1.

[Comparative Example 2]
A positive photosensitive resin composition was similarly prepared using the solvent X-2 instead of the solvent C-1 used in Example 1.

[Comparative Example 3]
A positive photosensitive resin composition was similarly prepared using the solvent X-3 instead of the solvent C-1 used in Example 1.

[Comparative Example 4]
A positive photosensitive resin composition was similarly prepared using the solvent X-4 instead of the solvent C-1 used in Example 1.

[Comparative Example 5]
A positive photosensitive resin composition was similarly prepared using the phenol resin P-6 instead of the alkali-soluble resin P-1 used in Example 1 and the solvent X-5 instead of the solvent C-1. .

[Comparative Example 6]
A positive photosensitive resin composition was similarly prepared using the solvent X-6 instead of the solvent C-1 used in Example 1.

[Comparative Example 7]
A positive photosensitive resin composition was similarly prepared using the solvent X-7 instead of the solvent C-1 used in Example 1.

[Comparative Example 8]
A positive photosensitive resin composition was similarly prepared using the solvent X-8 instead of the solvent C-1 used in Example 1.

[Comparative Example 9]
A positive photosensitive resin composition was prepared in the same manner as in Example 28 except that a solvent in which C-1 and X-1 were mixed at a mass ratio of 10:90 was used.

[Comparative Example 10]
A positive photosensitive resin composition was prepared in the same manner as in Example 28 except that C-8 and X-1 were mixed at a mass ratio of 30:70 as the solvent.

[Comparative Example 11]
A positive photosensitive resin composition was prepared in the same manner as in Example 28 except that a solvent in which X-1 and X-3 were mixed at a mass ratio of 70:30 was used.

[Comparative Example 12]
A positive photosensitive resin composition was prepared in the same manner as in Example 28 except that a solvent in which X-1 and X-4 were mixed at a mass ratio of 70:30 was used.

[Comparative Example 13]
A positive photosensitive resin composition was prepared in the same manner as in Example 1 except that the viscosity of the varnish was adjusted to 4P.

[Comparative Example 14]
A positive photosensitive resin composition was prepared in the same manner as in Example 1 except that the viscosity of the varnish was adjusted to 22P.

<Method for measuring density of photosensitive resin composition>
3 cm ³ disposable over monkey syringe up the photosensitive resin composition 2.5 cm ³ measure was weighed and its mass by precision balance. The density of the photosensitive resin composition was calculated from the following (Formula 1).
Mass density ^(g / cm 3) = photosensitive resin composition of 2.5 cm ³ of the photosensitive resin composition ^{(g) /2.5 (cm 3)} ··· ( Equation 1)

<Measurement method of viscosity of photosensitive resin composition>
The photosensitive resin composition prepared above was weighed out by 2.0 cm ³ and the viscosity was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd .: RE-80, trade name).

<Evaluation of film thickness uniformity of photosensitive resin composition>
The photosensitive resin compositions obtained in the above Examples 1 to 35 and Comparative Examples 1 to 14 were subjected to a predetermined varnish at the center of an 8-inch silicon wafer using a spin coater (manufactured by Tokyo Electron: MARK-8, trade name). Was dispensed and spin-coated at a rotational speed such that the pre-baked film had a thickness of 9.0 μm. Pre-baking was performed on a hot plate at 125 ° C. for 180 seconds to form a pre-baked film. The film thickness was measured at a film thickness measuring device (Dainippon Screen Mfg. Co., Ltd .: Lambda Ace, trade name) with a 13-point film thickness at 15 mm intervals from -90 mm to 90 mm with the wafer center at the X coordinate of 0 mm. The maximum value and the minimum value of the average film thickness and the measured film thickness were obtained.

<Evaluation method of application area of photosensitive resin composition>
The photosensitive resin compositions obtained in the above Examples 1 to 35 and Comparative Examples 1 to 14 were subjected to a predetermined varnish at the center of an 8-inch silicon wafer using a spin coater (manufactured by Tokyo Electron: MARK-8, trade name). Was dispensed and spin-coated at a number of revolutions such that the pre-baked film had a thickness of 9.0 μm. Pre-baking was performed at 125 ° C. for 180 seconds on a hot plate to form a circular coating film.
The diameter of this coating film was measured with a ruler (manufactured by Mitutoyo Corporation: ABS Digimatic Caliper, trade name), and the coating area was calculated by the following formula.
Application area (cm ² ) = [(measured diameter (cm) / 2) ² × 3.14]
As this value increases, a pre-baked film having a predetermined film thickness can be obtained with a smaller discharge mass by the spin coating method.
In this example and comparative example, the coating area was evaluated as follows.
Application area 175 cm ² or more: ○
Application area less than 175 cm ² : ×

<Method for evaluating in-plane uniformity of photosensitive resin composition>
From the measured film thickness, in-plane uniformity was determined from the following formula.
In-plane uniformity (%) =
[[(Maximum value of measured film thickness) − (minimum value of measured film thickness)] / (average film thickness)] × 100
In this case, the in-plane uniformity was evaluated as follows.
In-plane uniformity 1.5% or less: ◎
In-plane uniformity exceeds 1.5% and 3% or less: ○
In-plane uniformity over 3% and below 5%:
In-plane uniformity exceeding 5%: ×

<Evaluation method of film thickness of edge portion of substrate of photosensitive resin composition>
From the measured film thickness, the film thickness of the edge portion of the substrate was determined from the following formula.
Edge thickness (nm) = (2 mm thickness from substrate edge)-(Average thickness)
In this case, the film thickness of the edge portion was evaluated as follows.
Edge thickness 200nm or less:
Edge thickness 200nm to 300nm: ○
Edge film thickness More than 300nm and less than 400nm: △
Edge thickness over 400 nm: ×
The density, coating area, in-plane uniformity and film thickness of the substrate edge of the prepared positive photosensitive resin compositions of Examples 1 to 35 and Comparative Examples 1 to 14 were evaluated, and the results are shown in Table 2.

From the results of Table 2, with (C) a vapor pressure at 25 ° C. is 10Pa～250Pa, and solvent density at 25 ° C. is ^{0.7g / cm 3 ~1.02g / cm 3} , the resin Examples 1 to 35 using a photosensitive resin composition for spin coating, wherein the density at 25 ° C. of the composition is 0.75 to 1.1 g / cm ³ and the viscosity at 25 ° C. is 5P to 20P. Compared with the comparative example, it can be seen that a pre-baked film having a predetermined film thickness can be obtained with a smaller discharge mass by the spin coating method, and the film thickness uniformity is also excellent.

  The photosensitive resin composition of the present invention includes a surface protective film for semiconductor devices, an interlayer insulating film, an insulating film for rewiring, a protective film for flip chip devices, a protective film for devices having a bump structure, and an interlayer insulating film for multilayer circuits It can be suitably used as a cover coat of a flexible copper-clad plate, a solder resist film, a liquid crystal alignment film, and the like.

Claims (14)

(A) an alkali-soluble resin;
The solvent and (C) vapor at 25 ° C. pressure is 10Pa～250Pa, and density at 25 ° C. is ^{0.7g / cm 3 ~1.02g / cm 3} ; (B) a photoacid generator;
A spin-coating a photosensitive resin composition comprising, density at 25 ° C. of the spin-coating a photosensitive resin composition ^is a ^{0.75g / cm 3 ~1.1g / cm 3} , and the spin-coating The photosensitive resin composition for spin coating, wherein the photosensitive resin composition for coating has a viscosity at 25 ° C. of 0.5 Pa · s to 2 Pa · s. Wherein (C) the density of the solvent ^{is 0.8g / cm 3 ~0.95g / cm 3} , a spinning photosensitive resin composition of claim 1.   The said photosensitive resin composition for spin coats contains the said (C) solvent of 30 mass%-100 mass% with respect to the total mass of all the solvents contained in the said photosensitive resin composition for spin coats. Item 3. A photosensitive resin composition for spin coating according to item 1 or 2.   The photosensitive resin composition for spin coating according to any one of claims 1 to 3, wherein the (C) solvent is at least one selected from the group consisting of ketones, ethers, alcohols and glycols. The (C) solvent is represented by the following general formulas (1) to (4):

{In the formula, R ₁ and R ₂ are each independently an alkyl group having 1 to 9 carbon atoms, and the sum of the carbon atoms of R ₁ and R ₂ is 7 to 10. }

{In the formula, R ₃ and R ₄ are each independently an alkyl group having 1 to 11 carbon atoms, and the sum of the number of carbon atoms of R ₃ and R ₄ is 9 to 12. }

{Wherein R ₅ is an alkyl group having 5 to 10 carbon atoms. }

{In the formula, R ₆ and R ₇ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or the following general formula (5):

(Wherein R ₉ represents an alkyl group having 1 to 5 carbon atoms)
In which R ₆ and R ₇ are not both X, R ₈ represents a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, and n5 represents 1 ≦ It is a number satisfying n5 ≦ 3. }
The photosensitive resin composition for spin coating as described in any one of Claims 1-4 which is at least 1 selected from the group which consists of a compound represented by these.   The (C) solvent is 2-octanone, 2-nonanone, diisobutyl ketone, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol The photosensitive resin composition for spin coating according to any one of claims 1 to 5, which is at least one selected from the group consisting of propylene glycol dimethyl ether and dipropylene glycol methyl propyl ether.   The (A) alkali-soluble resin is at least one selected from the group consisting of an alkali-soluble polyimide, a polyimide precursor, a polybenzoxazole precursor, and a phenol resin, according to any one of claims 1 to 6. The photosensitive resin composition for spin coating as described. The (A) alkali-soluble resin is represented by the following general formula (6):

{Wherein, X ₁ and Y ₁ each independently represent a 2 to 8 valent organic group having 2 to 60 carbon atoms, and R ₁₀ and R ₁₁ each independently represent a hydrogen atom or a carbon atom. Represents an alkyl group of formulas 1 to 10, m1 is an integer of 1 to 1000, n1 to n4 are each independently an integer of 0 to 4, and n1 and n3 are 0 ≦ (n1 + n3) ≦ 6. N2 and n4 satisfy 0 ≦ (n2 + n4) ≦ 6, and n1 to n4 do not all become zero. }
The photosensitive resin composition for spin coat as described in any one of Claims 1-7 containing resin represented by these, and / or a phenol resin.   The said (A) alkali-soluble resin contains 50 mass parts-150 mass parts phenol resin with respect to 100 mass parts of resin represented by the said General formula (6), The spin coat photosensitive of Claim 8 characterized by the above-mentioned. Resin composition.   The photosensitive resin composition for spin coating according to claim 1, wherein the (B) photoacid generator is a quinonediazide compound. below:
(A) spin-coating the photosensitive resin composition for spin coating according to any one of claims 1 to 10 on a substrate, and forming a photosensitive resin layer or a photosensitive film on the substrate;
(B) a step of exposing the photosensitive resin layer or the photosensitive film;
(C) A cured relief pattern comprising a step of removing a exposed portion or an unexposed portion of the photosensitive resin layer or photosensitive film with a developer to obtain a relief pattern; and (d) a step of heating the relief pattern. Manufacturing method.   A cured relief pattern obtained by the method according to claim 11.   A semiconductor device comprising a semiconductor element and a cured film provided on the semiconductor element, wherein the cured film is the cured relief pattern according to claim 12.   A display body device comprising a display body element and a cured film provided on the display body element, wherein the cured film is the cured relief pattern according to claim 12.